Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society (ACS)  

DOI： 10.1021/acs.organomet.2c00552

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Wiley  

DOI： 10.1002/ejic.202200655

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Other Link： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/ejic.202200655

Language：English   Publishing type：Research paper (scientific journal)  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：MDPI  

DOI： 10.3390/cryst12050605

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society  

DOI： 10.1021/acs.organomet.1c00695

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry  

Based on a new strategy of utilizing negative charges, a dibenzo[<italic>b</italic>,<italic>f</italic>]silepinyl dianion was synthesized and its hyperconjugative antiaromatic character is disclosed using NMR studies, large NICS_{<italic>zz</italic>} values, and ACID plots.

DOI： 10.1039/D1CC04434F

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society  

DOI： 10.1021/acs.organomet.0c00595

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry  

DOI： 10.1039/d0dt02496a

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society  

DOI： 10.1021/acs.organomet.0c00042

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society  

Investigation of the vinylidene rearrangement of phosphorus- and sulfur-substituted internal alkynes at a ruthenium center unveiled selective 1,2-migration of P- and S-substituents and unexpected dichromatic behaviors of a part of the resulting vinylidene complexes. Reactions of [CpRu(dppe)Cl] and R CCR , where R = alkyl, Ar and R = P(═O)(OR) , P(═O)R , SR, SO R, in the presence of NaBAr afforded the corresponding vinylidene complexes [CpRu{═C═C(R )(R )}(dppe)][BAr ], which were fully characterized by NMR and elemental analysis and, in some cases, X-ray diffraction analysis. C-labeling experiments disclosed selective migration of the P- and S-substituents. To our surprise, some of the products displayed dichromatic characters: although solutions of all the vinylidene products are yellow, several products were obtained as yellow and red crystals, others as red-purple crystals, and the rest as yellow crystals. UV-vis absorption spectra for the complexes displaying a dichromatic nature were recorded both in solution and in the solid state. X-ray diffraction analysis revealed that an intramolecular CH···O hydrogen bond between one of the methylene CH bonds in the dppe ligand and the E═O group (E = P, S) is present in the red and the red-purple crystals, which affects the conformation of the vinylidene ligand. In contrast, such hydrogen bonds were not observed in the yellow crystals. Time-dependent density functional theory (TD-DFT) analysis based on the crystal structures revealed that the structural changes of the vinylidene ligand upon the hydrogen bonding account for the dichromism. 1 2 1 2 F 1 2 F 13 2 2 2 4 4

DOI： 10.1021/acs.organomet.9b00856

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry  

<p>Introduction of dynamic bonds in both the hard and soft phases of thermoplastic elastomers enhances mechanical toughness by interphase synergistic interactions.</p>

DOI： 10.1039/c9ta07522d

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：Chem. Soc. Jpn.  

DOI： 10.1246/bcsj.20190090

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society  

DOI： 10.1021/acs.organomet.9b00019

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Wiley  

DOI： 10.1002/ejic.201800457

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society  

A series of sulfonium salts bearing a ferrocenyl chromophore, [FcMeArS][X] (Ar = Ph, 4-CH3C6H4
X = BF4, PF6, BArF 4), has been synthesized, which can generate an acid under 436 nm irradiation. The present study provides a rare example of ferrocene derivatives having a photoacid-generating function.

DOI： 10.1021/acs.organomet.8b00203

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Thieme  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry  

Rare examples of P-C reductive elimination in ruthenium complexes to generate phosphonium salts are presented. Triarylphosphines are converted into benzophospholium or phosphaphenalenium ligands via cyclometalation and 1,2-insertion of an alkyne followed by P-C reductive elimination. The intermediate in each step was successfully characterized using NMR and X-ray diffraction studies.

DOI： 10.1039/c8cc02539h

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

2-Acetylpyridine oxime esters are transformed into the corresponding alpha-oxygenated imines in an Ir(III) complex under mild conditions, where the selective metal coordination of the imino group effectively promotes tautomerization of the oxime esters into the N-oxyenamines and the subsequent rearrangement.

DOI： 10.1039/c7dt02528a

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

An oxidovanadium(IV) complex having a perrhenato ligand [VO(ReO4)(4,4'-(t)Bubpy)(2)][0.25SO(4)center dot 0.5ReO(4)] (4,4'-(t)Bubpy = 4,4'-di-tert-butyl-2,2'-bipyridine) efficiently catalyzes not only dehydrogenative oxidation of benzylic and propargylic mono-alcohols but also oxidative C-C bond cleavage of meso-1,2-diaryl-1,2-ethanediols under atmospheric molecular oxygen, affording the corresponding carbonyl compounds in good yield. (C) 2017 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2017.07.034

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

The first tellurocarbonyl complex with a half-sandwich structure [CpRuCl(CTe)(H(2)IMes)] was synthesized by a ligand substitution reaction. The practically complete series of the CpCE complexes [CpRuCl(CE)(H(2)IMes)] (E = O, S, Se, Te) were systematically explored. The tellurium atom in the CTe complex could be smoothly replaced with lighter chalcogen atoms.

DOI： 10.1039/c6dt04440a

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

DFT calculations on the transformation reaction of the internal alkynes [CpM(PhC equivalent to CC6H4R-p)-(dppe)](+) (M = Fe, Os; R = OMe, CO2Et, Cl) to the corresponding vinylidenes were carried out. It was found that the isomerization of all complexes of group 8 elements studied in the present work, as well as the Ru complex that had already been reported in our previous study, proceeds via a direct 1,2-aryl shift. For the Fe complex, two types of direct 1,2-aryl shifts (paths 1 and 2), which depend on the orientation of the alkyne/vinylidene parts, were found, and the activation free energy of path 2 is smaller than that of path 1. As for the Os complex, path 1 and another direct 1,2-shift, path 3, were obtained, and path 3 has smaller activation free energy, which is the case for the Ru complex. Therefore, the isomerization reaction of internal alkynes to vinylidenes proceeds through path 2 for the Fe complexes and path 3 for the Ru and Os complexes. The 1,2-migration reactions via path 2 for the Fe complex and path 3 for the Os complex were found to be nudeophilic, which is based on an orbital interaction corresponding to an electron transfer from a carbon on the migrating group to the atom being migrated, as well as for the Ru complexes. To evaluate the stability of the alkyne and vinylidene complexes, orbital interaction energies between an organometallic complex part and an internal alkyne or a vinylidene moiety were calculated by natural bond orbital (NBO) analysis. It was revealed that the Os complex has the strongest interaction, followed by the Ru and Fe complexes. Namely, both the internal alkyne complexes and the vinylidene complexes are more stabilized in a heavier metal complex The activation free energy for migration of the aryl or phenyl group is actually the lowest for the Fe complex among the three metals. These findings contribute to the development of the synthetic strategy of vinylidenes from internal alkynes.

DOI： 10.1021/om501280c

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

Reaction of [(eta(6)-C6Me6)RuCl(Ph)(PMe3)] with internal alkynes in the presence of NaBAr4F gave rise to the 1,4-Ru migration to form the o-vinylaryl complex, providing the first example of 1,4-metal migration of a group 8 metal center; in one case further isomerization to an eta(3)-allyl complex was observed.

DOI： 10.1039/c4cc09699a

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

Competition between vinylidene rearrangement/1,1-insertion and 1,2-alkyne insertion into the Ir-Ar bond of [(CpIr)-Ir-star( ppy-F-4)](+) was observed on reaction with diarylacetylenes. The former process afforded the iridacycle 2 via the subsequent 1,4-Ir migration, whereas the latter led to the pyridoisoquinolinium complex 4. Detailed analysis revealed that 4 isomerizes to 2 by heating at 50 degrees C.

DOI： 10.1039/c5dt02207j

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

A novel octanuclear vanadium(V) oxide cluster complex, [V8O20(4,4'-(t)Bubpy)(4)] (1), was synthesized and characterized by single-crystal X-ray structure analysis to reveal that 1 has an unprecedented neutral V8O20 core. An unexpected interconversion between 1 and the methoxo(oxo)vanadium(V) cluster complex, [V4O8(OMe)(4)(4,4'-(t)Bubpy)(2)] (2), was observed upon changes in the solvent systems.

DOI： 10.1021/ic4031393

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry  

The reaction of [Cp*RhCl(Ph)(PR3)] (R = Ph or Me) with internal alkynes in the presence of NaBArF 4 affords the o-vinylaryl complex with a Rh-(vinyl CH) agostic interaction by way of the alkyne insertion followed by 1,4-rhodium migration, providing the first example of the 1,4-migration of a Rh(III) center. © 2013 Royal Society of Chemistry.

DOI： 10.1039/c3cc46700g

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

Photolysis of the cyclotriphosphato complex (PPN)[Ru(P3O9)(eta(6)-C6H6)] (2) with bpy (2,2'-bipyridyl) in alcohols generated a violet solution of (PPN)[Ru(P3O9)(bpy)-(ROH)] (3) with a labile alcohol ligand. Complexes 3 were readily oxidized during recrystallization to give the Ru(III) alkoxo complexes (PPN)[Ru(OR)(P3O9)(bpy)] (4). Treatment of 3 with internal alkynes led to selective formation of eta(2)-alkyne complexes (PPN)[Ru(P3O9)(bpy)(eta(2)-RC CR')] (7), which did not undergo vinylidene rearrangement under heating and photoirradiation conditions in contrast to its dppe analogues. On the other hand, diphenylacetylene complex 7c (R = R' = Ph) gave the alpha-ketocarbene complex (PPN)[Ru(P3O9)(bpy)(= CPhCOPh)] (8) on reaction with m-CPBA. This observation provides a very rare example for the direct and controlled oxidation of a coordinated alkyne ligand. Reactions of 3 with the terminal alkynes in alcohols and in DMF afforded the alkoxycarbene complexes (PPN)[Ru(P3O9)(bpy){= C(OR)CH2CR'}] (9) and the carbonyl complex (PPN)[Ru(P3O9)(CO)(bpy)] (12), respectively, presumably by way of vinylidene intermediates.

DOI： 10.1021/om3009926

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

Internal alkyne-to-vinylidene isomerization in the Ru complexes ([CpRu(eta(2)-PhC equivalent to CC6H4R-p)(dppe)](+) (Cp = eta(5)-C5H5; dppe = Ph2PCH2CH2PPh2; R = OMe, Cl, CO2Et)) has been investigated using a combination of quantum mechanics and molecular mechanics methods (QM/MM), such as ONIOM(B3PW91:UFF), and density functional theory (DFT) calculations. Three kinds of model systems (I-III), each having a different QM region for the ONIOM method, revealed that considering both the quantum effect of the substituent of the aryl group in the eta(2)-allcyne ligand and that of the phenyl groups in the dppe ligand is essential for a correct understanding of this reaction. Several plausible mechanisms have been analyzed by using DFT calculations with the B3PW91 functional. It was found that the isomerization of three complexes (R = OMe, CO2Et, and Cl) proceeds via a direct 1,2-shift in all cases. The most favorable process in energy was path 3, which involves the orientation change of the alkyne ligand in the transition state. The activation energies were calculated to be 13.7, 15.0, and 16.4 kcal/mol, respectively, for the three complexes. Donor-acceptor analysis demonstrated that the aryl 1,2-shift is a nucleophilic reaction. Furthermore, our calculation results indicated that an electron-donating substituent on the aryl group stabilizes the positive charge on the accepting carbon rather than that on the migrating aryl group itself at the transition state. Therefore, unlike the general nucleophilic reaction, the less-electron-donating aryl group has an advantage in the migration.

DOI： 10.1021/ja308018b

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

The reaction of diphenylacetylene at a cationic ruthenium complex with a dppm (Ph2PCH2PPh2) ligand, [CpRu(dppm)](+), has been studied to reveal essentially for the first time the existence of an equilibrium between an eta(2)-internal alkyne and eta(1)-disubstituted vinylidene at a transition metal center. The reaction mixture at 70 degrees C for 69 h unexpectedly afforded a coupling product of diphenylacetylene and the dppm ligand, an (alkenylphosphonio)phenyl complex [CpRu{Ph2PCH2P(C6H4)Ph(eta(2)-C(Ph)=CHPh)}](+) with the extremely rare coordination mode of kappa P-1,eta C-1,eta C-2,C'. The (alkenylphosphonio)phenyl complex further undergoes inversion of the coordination face of the alkene moiety at p-xylene reflux temperature. Both isomers of (alkenylphosphonio)phenyl complexes as well as the intermediary eta(2)-internal alkyne and eta(1)-disubstituted vinylidene complexes were fully characterized spectroscopically and crystallographically. By considering the structure of the (alkenylphosphonio)phenyl complexes obtained, the coupling reaction has been proposed to involve the attack of a phosphorus atom on the coordinated diphenylacetylene, which is in equilibrium with an eta(1)-diphenylvinylidene ligand, and the C-H bond activation of a phenyl group on the cationic phosphorus atom leading to the products. Theoretical calculations support the proposed mechanism.

DOI： 10.1021/om3004948

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

Details of complex formation kinetics are reported for tetrakis(2-hydroxyethyl) substituted cyclen (L-1) and cyclam (L-2) with Cu(II) and Co(II). Stopped-flow kinetics and spectroscopic titration methods were employed for the activation parameters and stability constants, respectively. X-ray studies revealed that the pendant 2-hydroxyethyl groups are not equivalent: two are folded over the macrocycle and maintained by intramolecular hydrogen bonds while the others are extended and pointed away from the macrocyclic cavity. Complex formation kinetics and spectroscopic titration were performed in aqueous acidic buffer solutions. Thermodynamic and kinetic parameters revealed that the ring size of the macrocycles plays an extremely important role for each metal ion studied. Stopped-flow kinetic measurements explained the mechanism of the complex formation process of both Cu(II) and Co(II) which proceed in outer-sphere interactions with ligands. There are two steps in the complex formation of the system studied. The initial step is a second order reaction between the metal ion and macrocycle with a second order rate constant. (C) 2011 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.saa.2011.08.078

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

A series of cyanamido-bridged di- and tetraruthenium complexes with eta(6)-C6Me6 ligands have been synthesized, and their interconversion reactions have been investigated. Facile interconversion between the mu(2)-kappa N,kappa N and mu(2)-kappa N,kappa N' coordination modes of NCNH ligands at a dimetallic core has been observed for the first time.

DOI： 10.1246/cl.2011.1167

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The cationic disubstituted vinylideneruthenium complexes [CpRu{=C=C(Ph)R}(dppe)][BAr4F], which are prepared directly from internal alkynes via 1,2-migration of carbon substituents, are shown to undergo disubstituted vinylidene-to-internal alkyne isomerization on reaction with a monophosphine. The observation provides the first examples in which the reversible conversion between internal alkynes and disubstituted vinylidenes is experimentally confirmed, and the kinetic and mechnistic investigations indicated that an uncommon electrophilic 1,2-migration of the carbon substituents takes place in the internal alkyne-disubstituted vinylidene interconversion.

DOI： 10.1021/om101109c

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The first five-coordinate selenocarbonyl complex, [RuCl(2)(CSe)(H(2)IMes)(PCy(3))] (2-Cse; H(2)IMes = 1,3-dimesitylimidazolin-2-ylidene), and the tellurocarbonyl complex [RuCl(2)(CTe)(H(2)IMes)(dmap)(2)] (3-CTe; dmap = 4-(dimethylamino)pyridine) was obtained by selenium and tellurium atom transfer reaction to the carbido complex [RuCl(2)(C)(H(2)IMes)(PCy(3))]. Systematic elucidation of the complete series of chalcogenocarbonyl complexes revealed that tellurocarbonyl complex 3-CTe is a potential tellurium atom transfer reagent

DOI： 10.1021/om901029w

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Cationic ruthenium and iron complexes [CpM(PP)](+) (Cp = eta(5)-C5H5; M = Ru and Fe; PP = Ph2PCH2CH2PPh2, 2PPh(3)) can affect vinylidene rearrangement of general internal alkynes via the 1,2-migration of aryl and alkyl groups. Judging from the migratory aptitude of substituted aryl groups, the present reaction is viewed as an uncommon electrophilic rearrangement.

DOI： 10.1246/cl.2009.534

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Core expansion reactions of di- and tetrairidium complexes [Cp*Ir(mu(2)-NCN-N,N)](2) (1; Cp* = eta(5)-C5Me5), [Cp*Ir(mu(3)-NCN-N,N,N)](4) (2), and phosphine derivatives of 1 have been investigated, and it has been revealed that cyanamido ligands in these complexes can change their coordination modes flexibly on reactions with a second transition metal complex. Treatment of diiridium complex 1 with [Cp*IrCl2](2) gives the tetrairidium complex [(Cp*Ir)(2)(mu(3)-NCN-N,N,N')(2)(IrCp*Cl-2)(2)] (6) with mu(3)-kappa N,kappa N,kappa N' cyanoimido(2-) ligands. On the other hand, the reaction of 1 with [PdCl(eta(3)-C3H5)](2) affords the NCN-bridged Ir2Pd4 hexanuclear complex [(Cp*IrCl)(2)(mu(4)-NCN-N,N,N',N')(2){Pd-2(mu-Cl)(eta(3)-C3H5)(2)}(2)] (7) and Ir4Pd4 octanuclear complex [(Cp*Ir)(4)(mu(4)-NCN-N,N,N,N')(4){PdCl(eta(3)-C3H5)}(4)] (8). The NCN-bridges in 7 provide the first example of the crystallographically determined mu(4)-kappa N,kappa N,kappa N',kappa N' carbodiimido(2-) ligand. Complex 8 with mu(4)-kappa N,kappa N,kappa N,kappa N' cyanoimido(2-) ligands can also be synthesized selectively by the reaction of the parent cubane complex 2 with [PdCl(eta(3)-C3H5)](2). Diphosphine derivative of 1, [{Cp*Ir(mu(2)-NCN)}(2)(mu-dppm)] (4; dppm = Ph2PCH2PPh2), behaves differently on reactions with [PdCl(eta(3)-C3H5)](2) and [MCl(cod)](2) (cod = cycloocta-1,5-diene) to form the NCN-bridged Ir2M2 (M = Pd, Rh, Ir) tetranuclear complexes [(Cp*Ir)(2)(mu(3)-NCN-N,N,N')(2)(PdCl(mu(3)-C3H5)}(2)(mu-dppm)] (9) and [(Cp*Ir)(2)(mu(3)-NCN-N,N,N')(2)(MCl(cod)}(2)(mu-dppm)] (11a, M = Rh; 11b, M = Ir), respectively. The molecular structures for 6, 7, 8, 11a, and 11b have been determined by single-crystal X-ray analyses.

DOI： 10.1021/ic8017503

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

Novel neutral mixed-ligand lr(N boolean AND C boolean AND N)(N boolean AND C)X complexes (N boolean AND C boolean AND N = 1, 3-bis (3-methylpyrazolyl)benzene (bpzb), 1,5-dimethyl-2,4-bis(3-methylpyrazolyl)benzene (dmbpzb), and 1,5-difluoro-2,4-bis(3-methylpyrazolyl)benzene (dfbpzb); N boolean AND C = 2-phenyl pyridine (ppy); and X = Cl or CN) have been synthesized and characterized. An X-ray single-crystal structure of the complex lr(dmbpzb)(ppy)Cl shows that the nitrogen atom in the ppy ligand occupied the trans position to the carbon atom in the tridentate N boolean AND C boolean AND N ligand of dmbpzb with the lr-C bond length of 1.94(1) angstrom, whereas the coordinating carbon atom occupied the trans position of chlorine. Electrochemical data show that the complexes exhibit an oxidation lr(III/IV) process in the potential range of +0.5 similar to 0.9 V and two irreversible reductions at approximately -2.6 and -3.0 V against Fc(0)/Fc(+), respectively. All of the lr(III) complexes do not emit phosphorescence at room temperature, although strong phosphorescence is exhibited at 77 K with the 0-0 transition centered at around 450 nm and lifetimes of 3-14 mu s. DFT calculations indicate that the HOMOs are mainly localized on iridium 5d pi and chlorine p pi*, whereas the LUMOs are mainly from the ppy ligand pi* orbitals. The phosphorescence originates from a (LC)-L-3 state mixed with the (MLCT)-M-3 and (XLCT)-X-3 ones. Temperature-dependent lifetime measurements of lr(dfbpzb)(ppy)Cl reveal the existence of a thermal deactivation process with a low activation energy (1720 cm(-1)) and very high frequency factor (2.3 x 10(13) s(-1)). An unrestricted density functional theory indicates that the dd state, in which both the lr-N (pyrazolyl) bond lengths increase considerably, exists almost at the same energy as that for the phosphorescent state. A thorough analysis based on the potential energy surfaces for the T-1 and S-0 states allows us to determine the reaction pathway responsible for this thermal deactivation. The calculated activation energies of 1600 similar to 1800 cm(-1) are in excellent agreement with the observed values.

DOI： 10.1021/ic800196s

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The reaction of the mono(hydrosulfido) iridium complex [Cp*IrH(SH)(PPh3)] (1, Cp* = eta(5)-C5Me5) with [Cp*MCl2(NO)] (2, M = Mo, W) afforded the mono(sulfido)-bridged Ir-Mo and Ir-W heterodinuclear complexes [Cp*IrH(PPh3)(mu-S)MCl(NO)Cp*] (3a and 3a', M = Mo; 3b and 3b', M = W) as a 2:1 mixture of diastereomers. Abstraction of the hydrido ligand in both 3a and 3a' with [Ph3C][BF4] in CH2Cl2-MeCN underwent stereoselectively to give the R-1r,R-M0/S-1r,S-M0 pair of the cationic acetonitrile complex [Cp*Ir(NC-Me)(PPh3)(mu-S)MoCl(NO)Cp*][BF4] (4). The stereochemical course for the formation of 4 from the major isomer 3a was confirmed to be inversion at the iridium center by X-ray crystallographic studies. Ligand substitution experiment of 4 with CD3CN revealed that the stereochemistry of 4 is controlled thermodynamically. (C) 2008 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.inoche.2008.02.026

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The reaction of the group 9 bis(hydrosulfido) complexes [Cp*M(SH)(2)(PMe3)] (M = Rh, Ir; Cp* = eta(5)-C5Me5) with the group 6 nitrosyl complexes [CP*M'Cl-2(NO)] (M' = Mo", W) in the presence of NEt3 affords a series of bis(sulfido)bridged early-late heterobimetallic (ELHB) complexes [CP*M(PMe3)(mu-S)(2)M'(NO)Cp*] (2a, M = Rh, M' = Mo; 2b, M = Rh, M' = W; 3a, M = Ir, M' = Mo; 3b, M = Ir, M' = W). Similar reactions of the group 10 bis(hydrosulfido) complexes [M(SH)(2)(dppe)] (M = Pd, Pt; dppe = Ph2P(CH2)(2)PPh2), [Pt(SH)(2)(dppp)] (dppp = Ph2P(CH2)(3)Pph(2)), and [M(SH)(2)(dpmb)] (dpmb = o-C6H4(CH2PPh2)(2)) give the group 10-group 6 ELHB complexes [(dppe)M(mu-S)(2)M'(NO)Cp*] (M = Pd, Pt; M'= Mo, W), [(dppp)Pt(mu-S)(2)M'(NO)Cp*] (6a, M'= Mo; 6b, M'= W), and [(dpmb)M(mu-S)(2)M'(NO)Cp*] (M = Pd, Pt; M' = Mo, W), respectively. Cyclic voltammetric measurements reveal that these ELHB complexes undergo reversible one-electron oxidation at the group 6 metal center, which is consistent with isolation of the single-electron oxidation products [Cp*M(PMe3)(mu-S)(2)M'(NO)Cp*][PF6] (M = Rh, Ir; M' = Mo, W). Upon treatment of 2b and 3b with ROTf (R = Me, Et; OTf = OSO(2)CFA the 0 atom of the terminal nitrosyl ligand is readily alkylated to form the alkoxyimido complexes such as [Cp*Rh(PMe3)(mu-S)(2)W(NOMe)Cp*][OTf]. In contrast, methylation of the Rh-, Ir-, and Pt-Mo complexes 2a, 3a, and 6a results in S-methylation, giving the methanethiolato complexes [Cp*M(PMe3)(mu-SMe)(mu-S)Mo(NO)Cp*][BPh4] (M = Rh, Ir) and [(dppp)Pt(mu-SMe)(mu-S)Mo(NO)Cp*][OTf], respectively. The Pt-W complex 6b undergoes either S- or O-methylation to form a mixture of [(dppp)Pt(mu-SMe)(mu-S)W(NO)Cp*][OTf] and [(dppp)Pt(mu-S)(2)W(NOMe)Cp*][OTf]. These observations indicate that O-alkylation and one-electron oxidation of the dinuclear nitrosyl complexes are facilitated by a common effect, i.e., donation of electrons from the group 9 or 10 metal center, where the group 9 metals behave as the more effective electron donor.

DOI： 10.1021/ic702309h

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The iridium hydrosulfido complexes [Cp*IrH(SH)(PPh3)] (Cp* = eta(5)-C5Me5) and [Cp*Ir(SH)(2)(PMe3)] were found to serve as effective building blocks for the synthesis of mono- and bis(sulfido)-bridged heterodinuclear complexes with a high-valent tungsten or rhenium-imido center.

DOI： 10.1246/cl.2007.622

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The reaction Of [Cp*CoI2](2) (1b) with 2 equiv of NaNCNH affords the 16-membered macrocyclic NCNH-bridged tetracobalt(III) complex [Cp*CoI(mu(2)-NCNH-N,N')](4) (2b), while that with 2 equiv of Na2NCN yields the C-3-elongated cubane-like NCN-bridged tetracobalt(III) complex [Cp*Co(mu(3)-NCN-N,N,N')(3)(CoCp*)(3)(mu(3)-NCN-N,N,N)] (4b). Treatment of [Cp*RhCl2](2) (1c) with 2 equiv of NaNCNH gives the C-3-elongated cubane-like tetrarhodium(III) complex [Cp*Rh(mu(3)-NCN-N,N,N')(3)(RhCp*)(3)(mu(3)-NCN-N,N,N)] (4c) via the macrocyclic complex [Cp*RhCl(mu(2)-NCNH-N,N')](4) (2c). On the other hand, the reaction of [Cp*CoCl](2) (7) with Na2NCN affords the anionic bis(NCN)-capped tricobalt(II) complex Na[(CP*CO)(3)(mu(3)-NCN-N,N,N)(2)] (6). The molecular structures of complexes 2b center dot CH2Cl2 and 4c - 2C(6)H(6) have been confirmed by X-ray analyses. The electrochemical properties of these types of NCN-bridged group 9 metal complexes have also been examined. (c) 2006 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.jorganchem.2006.08.054

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The tetraruthenium complex [Cp*RuCl](4) (Cp* = eta(5)-C5Me5) reacts with Na2NCN to afford the anionic bis(cyanamido)-capped triruthenium complex [(Cp*Ru)(3)(mu(3)-NCN)(2)](-) (2(-)), which undergoes single electron oxidation to form [(Cp*Ru)(3)(mu(3)-NCN)(2)] upon workup with 1 equiv. of [Cp2Fe](PF6) (Cp = eta(5)-C5H5). Treatment of 2(-) with 1 equiv. of HCl at room temperature leads to the protonation of one of the Ru-Ru edges to give the hydrido-bridged complex [(Cp*Ru)(3)(mu-H)(mu-NCN)(2)], while the cationic side-on NCNH2 complex [(Cp*Ru)(3)(mu-Cl)(mu(3)-NCN)(mu(3)-NCNH2-1 kappa C,N:2 kappa C:3 kappa N)]Cl (5) is obtained by the reaction of 2- with an excess amount of HCl at -78 degrees C. On the other hand, the reaction of 2(-) with BR3 (R = Et, Ph) results in the ligation of two BR3 molecules to the terminal nitrogen atoms of the cyanamido ligands to yield the bis(borane) adduct (PPN)[(Cp*Ru)(3){(mu(4)-NCN)(BR3)}(2)] (6,PPN = Ph3PNPPPh3). 6b (R = Et) slowly liberates one BEt3 molecule in acetone to give the mono(borane) adduct (PPN) [(Cp*Ru)(3)(mu(3)-NCN){(mu(4)-NCN)(BEt3)}] (7). 2(-) is also shown to react with [AuCl(PPh3)] or PhCOCl to afford the tetranuclear heterometallic complex [(Cp*Ru)(3)(mu(3)-NCN){(mu(4)-NCN)(AuPPh3)}] ( 8) or the benzoylcyanamido complex [(Cp*Ru)(3)(mu(3)-NCN)(mu(3)-NCNCOPh)] in which the Au(PPh3)(+) or benzoyl fragment is bound to the terminal nitrogen atom of a cyanamido ligand. The molecular structures of PPN(+)2(-), 5 center dot C6H6, 7 and 8 center dot C6H6 have been determined by single-crystal X-ray analyses.

DOI： 10.1039/b708328a

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Novel mixed-ligand Ir( III) complexes, [ Ir( L)( N boolean AND C) X](n+) ( L) N boolean AND C boolean AND N or N boolean AND N boolean AND N; X) Cl, Br, I, CN, CH3CN, or - CCPh; n) 0 or 1), were synthesized, where N boolean AND C boolean AND N) bis( N-methylbenzimidazolyl) benzene ( Mebib) and bis( N-phenylbenzimidazolyl) benzene ( Phbib), N boolean AND N boolean AND N) bis( N-methylbenzimidazolyl) pyridine ( Mebip), and N boolean AND C) phenylpyridine ( ppy) derivatives. The X-ray crystal structures of [ Ir( Phbib)( ppy) Cl] and [ Ir( Mebib)( mppy) Cl] [ mppy) 5-methyl-2-( 2'-pyridyl) phenyl] indicate that the nitrogen atom of the ppy ligand is located trans to the coordinating carbon atom in Me- or Phbib, while the coordinating carbon atom in ppy occupies the trans position of Cl. [ Ir( Mebip)( ppy) Cl](+) showed a quasireversible Ir( III/IV) oxidation wave at + 1.05 V, while the Ir complexes, [ Ir( Mebib)( ppy) Cl], were oxidized at + 0.42 V versus Fc/Fc(+). The introduction of an Ir - C bond in [ Ir( Mebib)( ppy) Cl] induces a large potential shift of 0.63 V in a negative direction. Further, the oxidation potential of [ Ir( Mebib)( Rppy) X] was altered by the substitution of R, R', and X groups. Compared to the oxidation potential, the first reduction potential revealed an almost constant value at - 2.36 to - 2.46 V for [ Ir( L)( ppy) Cl] ( L) Mebib and Phbib) and - 1.52 V for [ Ir( Mebip)( ppy) Cl. The UV-vis spectra of [ Ir( Mebib)( R-ppy) X] show a clear singlet metal-to-ligand charge-transfer transition around 407 similar to 425 nm and a triplet metal-to-ligand charge-transfer transition at 498 similar to 523 nm. [ Ir( Mebip)( ppy) Cl] + emits at 610 nm with a luminescent quantum yield of Phi = 0.16 at room temperature. The phosphorescence of [ Ir( Mebib)( ppy) X] was observed at 526 nm for X) CN and 555 nm for X) Cl with the high luminescent quantum yields, Phi = 0.77 similar to 0.86, at room temperature. [ Ir( Phbib)( ppy) Cl] shows the emission at 559 nm with a luminescent quantum yield of) 0.95, which is an unprecedentedly high value compared to those of other emissive metal complexes. Compared to the luminescent quantum yields of the Ir( ppy) 2( L) derivatives and [ Ir( Mebip)( ppy) Cl](+), the neutral Ir complexes, [ Ir( L)( R-ppy) X] ( L) Me- or Phbib), reveal very high quantum yields and large radiative rate constants ( k(r)) ranging from 3.4 x 10(5) to 5.5 x 10(5) s(-1). The density functional theory calculation suggests that these Ir complexes possess dominantly metal-to-ligand charge-transfer and halide-to-ligand charge-transfer excited states. The mechanism for a high phosphorescence yield in [ Ir( bib)( ppy) X] is discussed herein from the perspective of the theoretical consideration of radiative rate constants using perturbation theory and a one-center spin - orbit coupling approximation.

DOI： 10.1021/ic060796o

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We have isolated a new dinuclear palladium(II) complex containing 1,1,2,2-tetraacetylethanato (taet) and 1,1,1,5,5,5-hexafluoroacetylacetonato (hfac) ligands, [(hfac)Pd(C,O-taet)Pd(hfac)] (2b), whose crystallographic study has revealed that taet is coordinated to each palladium center as a kappa C-2,O ligand to form a five-membered chelate ring. Complex 2b provides the first example of the kappa C-2,O:(KC)-C-2',O' coordination mode of beta-diketonato ligand, which slowly tautomerizes to [(hfac)Pd(O,O-taet)Pd(hfac)] (2a).

DOI： 10.1246/cl.2006.936

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DOI： 10.24789/00001219

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A series of novel emissive Ir(III) complexes having the coordination environments of [Ir(N boolean AND N boolean AND N)(2)](3+), [Ir(N boolean AND N boolean AND N)-(N boolean AND N)Cl](2+), and [Ir(N boolean AND N boolean AND N)(N boolean AND C boolean AND N)](2+) with 2,6-bis(1-methyl-benzimidazol-2-yl)pyridine (L1, N boolean AND N boolean AND N), 1,3-bis-(1-methyl-benzimidazol-2-yl)benzene (L2H, N boolean AND C boolean AND N), 4'-(4-methylphenyl)-2,2':6',2"-terpyridine (ttpy, N boolean AND N boolean AND N), and 2,2'-bipyridine (bpy, N boolean AND N) have been synthesized and their photophysical and electrochemical properties studied. The Ir(III) complexes exhibited phosphorescent emissions in the 500-600 nm region, with lifetimes ranging from approximately 1-10 mu s at 295 K. Analysis of the 0-0 energies and the redox potentials indicated that the lowest excited state of [Ir(L1)(L2)](2+) possessed the highest contribution of (MLCT)-M-3 (MLCT = metal-to-ligand charge transfer) among the Ir(III) complexes, reflecting the sigma-donating ability of the tridentate ligand, ttpy &lt; L1 &lt; L2. The emission quantum yields (Phi) of the Ir(III) complexes ranged from 0.037 to 0.19, and the highest Phi value (0.19) was obtained for [Ir(L1)(bpy)Cl](2+). Radiative rate constants (k(r)) were 1.2 x 10(4) S-1 for [Ir(ttpy)(2)](3+), 3.7 x 10(4) S-1 for [Ir(L1)(bpy)Cl](2+), 3.8 x 10(4) S-1 for [Ir(ttpy)(bpy)Cl](2+), 3.9 X 10(4) S-1 for [Ir(L1)(2)](3+), and 6.6 x 10(4) S-1 for [Ir(L1)(L2)](2+). The highest radiative rate for [Ir(L1)(L2)](2+) With the highest contribution of (MLCT)-M-3 could be explained in terms of the singlet-triplet mixing induced by spin-orbit coupling of 5d electrons in the MLCT electronic configurations.

DOI： 10.1021/ic048622z

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[Cp*IrCl2](2) reacts with 2 equiv of Na2NCN to afford the NCN-bridged diiridium complex [Cp*Ir(&mu;(2)-NCN-N,N)](2) (5), which undergoes further reactions with donor molecules such as CO and phosphines. Complex 5 works as an excellent building block for the synthesis of the NCN-capped heterotrinuclear complexes [(Cp*Ir)(2)(ML)(&mu;(3)-NCN-N,N,N)(2)](+) (ML = Rh(cod), CpRu, Pd(&eta;(3)-C3H5)) on reactions with cationic group 8-10 metal complexes such as [Rh(cod)(acetone)](+), [CpRu(MeCN)(3)](+), and [Pd(&eta;(3)-C3H5)(acetone)(n)](+), while the dimerization of 5 leads to the cubane-type tetrairidium complex [Cp*Ir(&mu;(3)-NCN-N,N,N)](4).

DOI： 10.1021/om048978i

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The reaction of the cyclotetraphosphate ion (P4O124-) with [Cp*TiCl3] (CP* = eta(5)-C5Me5) gives [(Cp*Ti)(2)(P4O12)(2)](2-) where the P4O12 ligands adopt a saddle conformation, while that with [(Cp*TiCl)(3)(mu-O)(3)] leads to [(Cp*Ti)(3)(mu-O)(3)(P4O12)](-) containing a crown form P4O12 ligand; both products feature their unique cage structures. On the other hand, the reactions of the cyclotriphosphate ion (P3O93-) with [(Cp*TiCl2)(2)(mu-O)] and [(Cp*TiCl)(3)(mu-O)(3)] afford [(Cp*Ti)(2)(mu-O)(P3O9)(2)](2-) and [(Cp*Ti)(3)(mu-O)(3)Cl(P3O9)](-), respectively, and in both cases the P3O9 ligands bridge two titanium centers with an eta(2):eta(1) mode.

DOI： 10.1021/ic049206h

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The cyclotetraphosphate ion (P4O124-) as a PPN (PPN = (PPh3)(2)N+) salt reacts with [MCl(cod)](2) (M = Rh, Ir; cod = 1,5-cyclooctadiene) to give the dinuclear complexes (PPN)(2)[{M(cod)}(2)-(P4O12)], in which the two metal moieties are situated trans to each other with respect to the P4O4 ring in the solid state. In solution, however, these complexes exist as mixtures of trans and cis isomers. On the other hand, the P4O124- ion reacts with 4 equiv of [Rh(cod)(MeCN)(x)](+) cation to give the tetranudear complex [Rh(cod)}(4)(P4O12)], where the four Rh(cod) fragments are bound to the P4O12 platform alternately on both sides of the P4O4 ring. Dinuclear P4O12 complexes of ruthenium and palladium are also synthesized.

DOI： 10.1021/ic0350382

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An Mn2+ complex with 2,2':6',2"-terpyridine (terpy) was found to promote the hydrolysis of NpN (NpN = diribonucleoside monophosphate diester) efficiently at pH 7.0 and 50 degreesC under ambient conditions. The structure of the Mn2+ complex involving a phosphodiester molecule, [(terpy)(dpp)Mn-II(mu-dpp)(2)Mn-II(dpp)(terpy)], dpp = diphenyl phosphate anion, was established by X-ray crystallography, and the coordination mode of Mn2+ to a phosphodiester molecule was considered.

DOI： 10.1246/bcsj.76.1813

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Treatment of 1-trimethylsilyloxy-1-cyclohexene (1a) in the presence of a catalytic amount of the acidic dihydrogen complex [RuCl(eta(2)-H-2)(dppe)(2)]OTf (4a) [dppe-1,2-bis(diphenylphosphino)ethane, OTf = OSO2CF3] (10 mol.%) under I atm of H-2 in anhydrous ClCD2CD2Cl at 50 degreesC for 8 h afforded cyclohexanone (3a) and Me3SiH in quantitative NMR yields. Silyl enol ethers such as 1-triethylsilyloxy-1-cyclohexene (1b), 1-t-butyldimethylsilyloxy-1-cyclohexene (1c), and other trimethylsilylethers (Id, le, and If) reacted similarly with H-2 to afford the corresponding ketones and trialkylsilanes. The direct proton transfer from H-2 to the trimethylsilyl enol ethers (1a and Id-1f) was confirmed by the experiments employing D-2 gas, where alpha-monodeuterated ketones (3a' and 3d'-3f) were obtained in high yields. The enantioselective protonation of prochiral silyl enol ethers with I atm of H-2 by employing [RUCl(eta(2)-H-2)((S)-BINAP)(2)]OTf (4e) [BINAP = 2,2'-bis(diphenylphosphino)-1, 1'-binaphthyl] and [RUCl(eta(2)-H-2)((R, R)CHIRAPHOS)(2)]OTf (4f) [CHIRAPHOS = 2,3-bis(diphenylphosphino)butane] showed that no enantioselectivity was observed in either catalytic or stoichiometric protonation reactions under various reaction conditions. The reaction of [RuHCl(dppe)(2)] (5a) with one equivalent of Me3SiOTf under 1 atm of H-2 produced rapidly 4a, concurrent with the formation of Me3SiH. Based on these studies, the mechanism for this novel hydrogenolysis of silyl enol ethers is proposed which involves heterolytic cleavage of the coordinated H-2 on the ruthenium atom caused by the nucleophilic attack of the oxygen atom of enol ethers to give ketones and Me3SiOTf, and the subsequent reaction of the resultant complex 5a with Me3SiOTf under I atm of H-2 to regenerate the original dihydrogen complex 4a. On the other hand, the stoichiometric reaction of a lithium enolate 6e with one equivalent of 4e at -78 degreesC in CH2Cl2 under I atm of H-2 afforded 2-methyl-1-tetralone (3e) with 75% ee (S) in &gt; 95% yield, together with the formation of [RuHCl((S)-BINAP)(2)] (5e). (C) 2003 Elsevier Science B.V. All rights reserved.

DOI： 10.1016/S0022-328X(03)00470-4

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The cyclotriphosphate ion (P3O93-) as a PPN [PPN = (Ph3P)(2)N+] salt reacted in CH2Cl2 at room temperature with the cationic solvated complexes of Pd(II) and Pt(II), [M(phosphine)(2)(Me2CO)(2)](2+) [M = Pd, Pt; phosphine = PPh3, PMePh2 1/2 Ph2P(CH2)(2)PPh2 (dppe), 1/2 Ph2P(CH2)(4)PPh2 (dppb)], to give the anionic P3O9 complexes (PPN)-[Pd(P3O9)(PPh3)(2)] (1), (PPN)[Pd(P3O9)(PMePh2)(2)] (2), (PPN)[Pt(P3O9)(PPh3)(2)] (3), (PPN)[Pt(P3O9)(PMePh2)(2)](4), (PPN)[Pt(P3O9)(dppe)] (5) and (PPN)[Pt(P3O9)(dppb)] (6). Crystallographic studies revealed that the P3O9 ligand in complexes 1-4 and 6 adopts a normal chair conformation and behaves as a pseudo-tridentate ligand with two normal M-O bonds and an additional weak M...O interaction. In 1 and 3, the terminal P3O9 oxygen atom weakly bound to the metal centre forms relatively strong intramolecular CH...O hydrogen bonds with the phosphine ligands. In contrast, the P3O9 ligand in 5 is bidentate and takes a pseudo-boat conformation. Complexes 1-6 are fluxional in solution and exhibit only one singlet due to the P3O9 ligand in the P-31-{H-1} NMR spectra at room temperature; the signals of complexes 4-6 split into two at -40 to -70 degreesC. The activation parameters for the fluxional behaviour of 6 were determined by the line shape analysis of the variable temperature P-31- {H-1} NMR spectra. The Pt(IV) complex (PPN)(2)[PtMe3(P3O9)] (7) was also synthesised and structurally characterised.

DOI： 10.1039/b301223a

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We have synthesized Mn-Pt nanoparticles using a chemical preparation based on a liquid-phase reaction caused by decomposition of organometallic precursors. The synthesized monodisperse Mn52.5Pt47.5 nanoparticles show an fcc crystalline structure and ferromagnetic properties even at the room temperature. Mn52.5Pt47.5, which is not ferromagnetic in a bulk form, shows a completely different physical property in nanoparticles.

DOI： 10.1021/jp026898r

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Treatment of [Cp*IrH(SH)(PMe3)] (CP* = eta(5)-C5Me5) with [IrCl2(NO)(PPh3)(2)] in the presence of triethylamine yielded the sulfido-bridged (IrIro)-Ir-II complex [Cp*Ir(PMe3)(mu-S)Ir(NO)(PPh3)], which further reacted with I-2 and triflic acid to give the diiodo complex [Cp*Ir(PMe3)(mu-I)(mu-S)IrI(NO)(PPh3)] and the hydrido complex [Cp*Ir(PMe3)(mu-H)(mu-S)Ir(NO)(PPh3)][OSO2CF3], respectively.

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DOI： 10.1002/anie.200351530

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Reactions of the bis(hydrosulfido) complexes [Cp*Rh(SH)(2)(PMe3)] (1a; Cp* = eta(5)-C5Me5) with [CpTiCl3] (Cp = eta(5)-C5H5) and [TiCl4(thf)(2)] in the presence of triethylamine led to the formation of the sulfido-bridged titanium-rhodium complexes [Cp*Rh(PMe3)(mu(2)-S)(2)TiClCp] (2a) and [Cp*Rh(PMe3)(mu(2)-S)(2)TiCl2] (3a), respectively. Complex 3a and its iridium analogue 3b were further converted into the bis(acetylacetonato) complexes [Cp*M(PMe3)(mu(2)-S)(2)Ti(acac)(2)] (4a, M = Rh; 4b, M = Ir) upon treatment with acetylacetone. The hydrosulfido complexes 1a and [Cp*Ir(SH)(2)(PMe3)] (1b) also reacted with [VCl3(thf)(3)] and [Mo(CO)(4)(nbd)] (nbd = 2,5-norbornadiene) to afford the cationic sulfido-bridged VM2 complexes [{Cp*M(PMe3)(mu(2)-S)(2)}(2)V](+) (5a(+), M = Rh; 5b(+), M = Ir) and the hydrosulfido-bridged MoM complexes [Cp*M(PMe3)(mu(2)-SH)(2)Mo(CO)(4)] (6a, M = Rh; 6b, M = Ir), respectively.

DOI： 10.1021/ic020105y

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DOI： 10.1021/ja017436e

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER INST PHYSICS  

We have successfully prepared Sm-Co composite nanoclusters using liquid-phase organometallic synthesis. The chemical composition was determined by quantitative x-ray fluorescence analysis and it is found that the composition of synthesized Sm-Co nanoclusters was Sm poor while the Sm-Co nanoclusters with required composition could be obtained in starting from the excess Sm(acac)(3). From the transmission electron microscopy measurements, the Sm-Co nanoclusters have the uniform size with the diameter of 9 nm. The crystalline structure was fcc which is different from that of bulk SmCo alloy with the same Sm and Co content. The magnetic property was observed by superconducting quantum interference magnetometer and shows the ferromagnetic characteristics. (C) 2002 American Institute of Physics.

DOI： 10.1063/1.1456407

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Treatment of [Rh(mu(2)-Cl)(cod)](2) (cod = 1,5-cyclooctadiene) with the hydrido-hydrogensulfido complex [Cp*IrH(SH)(PMe3)] (Cp* = eta(5)-C5Me5) in the presence of triethylamine afforded the hydrido-mono(sulfido) complex [Cp*Ir(PMe3)(mu(2)-H)(mu(3)-S){Rh(cod)}{RhCl(cod)}], whereas the corresponding reaction with the bis(hydrogensulfido) complex [Cp*Ir(SH)(2)(PMe3)] gave the bis(sulfido) complex [Cp*Ir(mu(3)-S)(2){Rh(cod)}(2)] with liberation of trimethylphosphine.

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The diaryl disulfide ligand in the thiolato-bridged diiridium(III) complexes [{Ir(mu-SC6H4 - nMe(n)CH(2))Cl(PPh3)}(2)-(mu-ArSSAr)] [1a, n = 1, Ar = C6H3Me2-2,6 (Xy); 1b, n = 2, Ar = C6H2Me3-2,4,6 (Mes)] is readily substituted by isocyanides, CO, hydroxylamine and hydrazines to afford the bis(isocyanide), bis( carbonyl) and bis( hydroxylamine) complexes [Ir(mu-SC6H4 (-) nMenCH2)Cl(PPh3)(L)](2) (2a, n = 1, L = XyNC; 2b, n = 2, L = XyNC; 3a, n = 1, L = (BuNC)-N-t; 3b, n = 2, L = (BuNC)-N-t; 4a, n = 1, L = CO; 4b, n = 2, L = CO; 7a, n = 1, L = NH2OH; 7b, n = 2, L = NH2OH) and the bridging hydrazine complexes [{Ir(mu-SC6H4 (-) (n) MenCH2)Cl(PPh3)}(2)(mu-NH2NR2)] (5a, n = 1, R = H; 5b, n = 2, R = H; 6, n = 1, R = Me), respectively. On the other hand, the reaction of 1b with MeLi resulted in reductive cleavage of the disulfide bond to give the coordinatively unsaturated diiridium() complex [Ir(mu-SC6H2Me2CH2)(SMes)(PPh3)](2) (8), which was further converted into the bis( carbonyl) complex [Ir(mu-SC6H2Me2CH2)(SMes)(PPh3)(CO)](2) (9) upon addition of CO. Treatment of 2b with AgPF6 led to the formation of the difluorophosphato-bridged complex [{Ir(mu-SC6H2Me2CH2)(PPh3)(XyNC)}(2)(mu-PF2O2)][PF6] (10). The structures of the thiairidaindan complexes 2b, 4a, 5a, 7a and 8-10 have been determined by X-ray crystallography.

DOI： 10.1039/b201591a

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The reaction of [(cod)M(m-OMe)](2) (M = Rh, Ir; cod = cycloocta-1,5-diene) with calix[4]arenes (LH4) in the molar ratio of 0.5-0.6:1 gave the rhodium and iridium pi-arene complexes [(cod)M(eta(6)-LH3)], while that in the molar ratio of 1.1-1.5:1 (M = Rh) led to the selective formation of the dinuclear complexes [{(cod)Rh}(2)(eta(6):eta(2)-LH2)] in which one of the Rh(cod)(+) fragments is coordinated by an eta(6)-aryl group and the other by two phenolic oxygen atoms; the stepwise synthesis of the Rh-Ir heterobimetallic analogue of the latter complex was further achieved.

DOI： 10.1039/b201992m

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Treatment of the hydrosulfido-bridged titanium-ruthenium heterobimetallic complex [Cp2Ti(mu (2)-SH)(2)RuCl(eta (5)-C5Me5)] (1; Cp = eta (5)-C5H5) with an excess of triethylamine followed by addition of [RuCl2(PPh3)(3)] and [{(cod)M}(2)- (mu (2)-Cl)(2)] (M = Rh, Ir; cod = 1,5-cyclooctadiene) led to the formation of the TiRu2 and TiRuM mixed-metal sulfido clusters [(CpTi){(eta (5)-C5H5)Ru}{Ru(PPh3)(2)}(mu (3)-S)(2)(mu (2)-Cl)(2)] (3) and [(CpTi){(eta (5)-C5Me5)Ru}{M(cod)}-(mu (3)-S)(2)(mu (2)-Cl)] (M = Rh (4a), Ir (4b)), respectively. On the other hand, the reactions of 1 with [M(PPh3)(4)] (M = Pd, Pt) afforded the TiRuM trinuclear clusters [(CpTiCl){(eta (5)-C5Me5)Ru}{M(PPh3)(2)}(mu (3)-S)(mu (2)-S)(mu (2)-H)] (M = Pd (5a), Pt (5b)) with an unprecendent M-3(mu (3)-S)(mu (2)-S) core. The detailed structures of these triangular clusters 3-5 have been determined by X-ray crystallograph. Crystal data: 3, triclinic, P (1) over bar, a = 12.448(4) Angstrom, b = 12.773-(4) Angstrom, c = 17.270(4) Angstrom, alpha = 100.16(2)degrees, beta = 99.93(2)degrees, gamma = 114.11(3)degrees, V = 2373(1) Angstrom (3), Z = 2; 4a, triclinic, P (1) over bar, a = 7.714(2) Angstrom, b = 11.598(3) Angstrom, c = 14.802(4) Angstrom, alpha = 80.46(2)degrees, beta = 82.53(2)degrees, gamma = 71.47(2)degrees, V = 1234.0(6) Angstrom (3), Z = 2; 4b, triclinic, P (1) over bar, a = 7.729(1) Angstrom, b = 11.577(2) Angstrom, c = 14.766(3) Angstrom, alpha = 80.14(1)degrees, beta = 82.71(1)degrees, gamma = 71.55(1)degrees, V = 1231.1(4) Angstrom (3), Z = 2; 5a, monoclinic, P2(1)/c, a = 11.369(2) Angstrom, b = 16.207(3) Angstrom. c = 26.116(2) Angstrom, beta = 102.29(1)degrees, V = 4701(1) Angstrom (3), Z = 4.

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The PdCl2(PPh3)(2)-Co-2(CO)(8) bimetallic catalyst was found to be effective for the carbonylation of ArI with CO/HSiEt3 to give benzyl silyl ethers as the major product, although neither PdCl2(PPh3)(2) nor Co-2(CO)(8) alone was catalytically active. Addition of NEt3 to the reaction system changed the distribution of the carbonylation products, where 1,2-diaryl-1,2-disiloxyethanes were obtained predominantly. The former reaction is suggested to proceed via the aldehyde intermediate, while a mechanism involving the aroylcobalt complex (ArCO)Co(CO)(3)(PPh3) formed by way of a Pd-Co bimetallic complex is proposed for the latter reaction. On the other hand, PdCl2(PCy3)(2) was found to work as a selective catalyst for the hydroformylation of internal alkynes to give the corresponding alpha,beta -unsaturated aldehydes, and the combined use of PdCl2(PCy3)(2) and Co-2(CO)(8) remarkably improved the catalytic activity with little change of the selectivity. Regio- and chemoselective hydroformylation of alkynes was achieved by using the PdCl2(PCy3)(2) and PdCl2(PCy3)(2)-Co-2(CO)(8) catalysts. (C) 2001 Elsevier Science B.V. All rights reserved.

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The heterobimetallic trinuclear sulfido clusters [(Cp*Ir)(2)(mu (3)-S)(2)MCl2] (M = Pd (3), Pt (4); Cp* = eta (5)-C5Me5) were synthesized from the dinuclear hydrogensulfido complex [Cp*IrCl(mu -SH)(2)IrCp*Cl] (2) and [MCl2(COD)] (COD = cycloocta-1,5-diene), while the reaction of 2 with [Pd(PPh3)(4)] afforded the cationic trinuclear cluster [(Cp*Ir)(2)(mu (3)-S)(2)PdCl(PPh3)]Cl (5). Clusters 3 and 4 reacted with PPh3 to give a series of mono and dicationic clusters including 5, while the dicationic clusters [(Cp*Ir)(2)(mu (3)-S)(2)M(dppe)][BPh4](2) (M = Pd (9), Pt (10); dppe = Ph2PCH2CH2PPh2) were obtained by the reaction with dppe followed by anion metathesis. The molecular structures of 5 . CH2Cl2, 9 . CH3COCH3, and 10 . CH3COCH3 were determined by X-ray crystallography. Clusters 3 and 4 were found to catalyze the addition of alcohols to alkynes to give the corresponding acetals. Internal 1-aryl-1-alkynes were transformed by cluster 3 into the corresponding 2,2-dialkoxy-1-arylalkanes with high regioselectivity up to 99:1, while cluster 4 was a much less regioselective catalyst. (C) 2001 Elsevier Science B.V. All rights reserved.

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The reaction of trans-[Mo(N-2)(2)(dppe)(2)] (1; dppe = Ph2PCH2CH2PPh2) with excess amounts of HC drop CLi(.)en (en = H2NCH2CH2NH2) afforded the five-coordinate Mo(0) mono(acetylene) complex [Mo(HC drop CH)(dppe)(2)] (2). Treatment of 2 with 2 mol of [Cp2Fe][BF4] (Cp = eta (5)-C5H5) in THF gave the Mo(II) acetylene complex trans-[MoF(HC drop CH)(dppe)(2)][BF4] while that in THF-MeCN followed by anion metathesis with NaOTf (OTf = OSO2CF3) led to the formation of the metallacyclopropene complex [Mo(eta (3)-CHCHPPh2CH2CH2PPh2-C,C',P)(MeCN)(2)(dppe)][OTf](2).

DOI： 10.1021/om0007623

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A series of heterobimetallic dinitrogen complexes containing group 6 and group 4 or 5 transition metals were synthesized by the reaction of the tungsten or molybdenum dinitrogen complexes cis-[W(N(2))(2)(PMe(2)Ph)(4)] (1) and trans-[M(N(2))(2)(dppe)(2)] (2) (M = W, Mo) with group 4 or group 5 compounds such as [CpTiCl(3)], [Cp(2)M&apos;Cl(2)] (M&apos; = Ti, Zr, Hf), or [Cp&apos;M&apos;Cl(4)] (Cp&apos; = Cp, Cp*; M&apos; = Nb, Ta). Crystallographic studies of the complexes thus obtained including [WCl(PMe(2)Ph)(4)(mu -N(2))TiCpCl(2)] and [WCl(PMe(2)Ph)(4)(mu -N(2))NbCpCl(3)] revealed that the M-N-N-M&apos; core is essentially linear, and the N-N bond is regarded to have the formal bond order of 2. Several mu -N(2) complexes with methyl ligands at the group 4 or 5 metal center were also obtained through the reaction of dinitrogen complexes 1 and 2a (M = W) with the methyl complexes [Cp(2)ZrMeCl], [TaMe(3)Cl(2)], and [NbMe(3)Cl(3)]. The reaction of the complex [WCl(dppe)(2)(mu -N(2))TiCpCl(2)] with Li(2)S(5) afforded the eta (2)-pentasulfido complex [WCl(dppe)(2)(mu -N(2))TiCpS(5)], where the eta (2)-S(5) ligand forms a six-membered chelate ring with the chair conformation. Protonation of the mu -N(2) complexes having PMe(2)Ph ligands gave NH(3) in moderate yield, concurrent with the formation of a small amount of NH(2)NH(2).

DOI： 10.1021/om000684j

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Chiral ruthenium(II) complexes, RuCl2(PPh3)(oxazolinylferrocenylphosphine), have been found to be effective catalysts for asymmetric hydrosilylation of ketoximes to give the corresponding primary amines in good yields with high enantioselectivities (up to 89% ee) after acid hydrolysis.

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Reactions of [Cp*Ir(SH)(2)(PMe3)] (1; Cp* = eta(5)-C5Me5) with [CpTiCl3](Cp = eta(5)-C5H5) and [TiCl4(thf)(2)] in the presence of triethylamine afforded the sulfido-bridged titanium-iridium heterobimetallic complexes [CpTiCl(mu(2)-S)(2)Ir-(PMe3)Cp*] (2) and [TiCl2(mu(2)-S)(2)Ir(PMe3)Cp*] (3), respectively.

DOI： 10.1021/om000417d

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Reactions of the cationic dirhodium and diiridium complexes [Cp*M(mu-Cl)(mu-SPri)(2)MCp*][OTf] (2, M = Rh; 3, M = Ir; Cp* = eta(5)-C5Me5, OTf = OSO2CF3) with terminal alkynes were investigated. Treatment of 2 and 3 with methyl propiolate afforded the cationic complexes [Cp*MCl(mu-SPri){mu-S(Pr-i)C=CHCOOMe}MCp*][OTf], (4, M = Rh; 5, M = Ir), in which the substituted vinyl ligand forms an M(1)-C-S-M(2) bridge and is further coordinated to the M(1) center at the carbonyl oxygen. On the other hand, [Cp*IrCl(mu-SPri){mu-C(SPri)=CH2} IrCp*][OTf] (8), in which the olefinic C=C bond of the alpha-(isopropylthio)vinyl ligand also works as an eta(2) ligand, was obtained by the reaction of 3 with acetylene gas. Complex 3 reacted with 1,1-diphenyl- or 1,1-ditolyl-2-propyn-1-ol to give the hydroxycarbene complexes [Cp*IrCl(mu-SPri)(2)Ir{=C(OH)CH=CAr2}Cp*][OTf](11) Ar = Ph; 12, Ar = Tol), while the reactions of complexes 2 and 3 with 3-butyn-1-ol and 4-pentyn-1-ol produced cyclic alkoxycarbene complexes [Cp*MCl(mu-SPri)(2)M {=(CH2)(n) + 2O}Cp*][OTf] (15, M = Rh, n = 1; 16, M = Ir, n = 1; 17, M = Ir, n = 2). All of the products are considered to be formed via the initial formation of a dinuclear vinylidene or allenylidene complex followed by the nucleophilic attack of an SPri ligand, H2O molecule, or the omega-OH group at the C-alpha atom of the vinylidene-type ligand. The intermediate vinylidene and allenylidene species are regarded to have higher reactivity in the nucleophilic addition reactions than the corresponding diruthenium complexes, and the difference in the reactivities is interpreted in terms of the extended Huckel molecular orbital calculations of model complexes. The molecular structures of complexes 3, 4, 5, [Cp*IrCl(mu-SPri){mu-C(SPri)=CH2}IrCp*][PF6].THF (8'.THF), 12, and 16 were determined by X-ray diffraction studies. (C) 2000 Elsevier Science S.G. All rights reserved.

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The reaction of the incomplete cubane-type duster [Mo-3(mu(3)-S)(mu-S)(3)(H2O)(9)]Cl-4 (1) and [Pt(dba)(2)] (dba = 1,5-diphenyl-1,4-pentadien-3-one) in MeOH gave a brown precipitate (4) that contains platinum and molybdenum in the atomic ratio of 1 :3. Further treatment of 4 with 3 equiv of dppe (dppe = 1, 2-bis(diphenylphosphino)ethane) gave the cubane type cluster [PtMo3(mu(3)-S)(4)Cl-4(dppc)(3)] (5) in 37% yield, whose molecular structure was unambiguously characterized by X-ray diffraction study of 5.2CH(2)ClCH(2)Cl.2H(2)O. A similar reaction of 4 with 4 equiv of dppe afforded the cationic cluster [PtMo3(mu(3)-S)(4)Cl-3(dppe)(4)]Cl (6) in 29% yield, which was characterized spectroscopically. The Pd-Mo and Ni-Mo analogues of the above Pt-Mo clusters, [PdMo3(mu(3)-S)(4)Cl .(dppe)(4)]Cl . CH2Cl2 (7) and [NiMo3(mu(3) -S)(4)Cl-4(dppe)(3)] (8), were also synthesized by the reactions of the corresponding aqua clusters with dppe.

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The molybdenum dinitrogen complex trans-[Mo(N(2))(2)(dppe)(2)] (2) reacted with 2-2.5 equiv of various beta-ketonitriles at room temperature to afford the (nitrido)(nitrile-enolato) complexes trans-(Mo(N)(NCCR(1)-COR(2))(dppe)(2)] (4; R(1) = H, R(2) = 4-MeOCOC(6)H(4), 4-ClC(6)H(4), 4-Tol, 4-MeOC(6)H(4), 2-C(4)H(3)O, 2-C(4)H(3)S, Pr(i); R(1) = CN, R(2) = Me, Ph; dppe = Ph(2)PCH(2)CH(2)PPh(2) via the C=N triple bond cleavage of the nitriles on the molybdenum center. On the other hand, the reaction of complex 2 with ? equiv of pivaloylacetonititrile at room temperature led to the isolation of the (alkylideneamido)(nitrile-enolato) complex trans-[Mo(NCHCH(2)COBu(l)(NCCHCOBu(l))(dppe)(2)] (5k), which further underwent the cleavage of the C=N double bond of the alkylideneamido ligand to give the corresponding (nitrido)(nitrile-enolato) complex trans-[Mo(N)(NCCHCOBu(l))(dppe)(2)] together with 4,4-dimethyl-1-penten-3-one. Furthermore, treatment of 2 with large excess amounts of 3-chlorobenzoylacetonitrile followed by anion metathesis with [NHEt(3)][OTf] (OTf = OSO(2)CF(3)) resulted in me isolation of the cationic (imido)(nitrile-enolato) complex trans-[Mo{NCH(2)CH(2)CO(C(6)H(4)Cl-4)}{NCCHCO-(C(6)H(4)Cl-4)}(dppe)(2)][OTf] (6c(+)[OTf](-)). The solid-state structures of 4h . 1.5C(2)H(4)Cl(2) (R(1) = CN, R(2) = Me), 5k . C(6)H(6), and 6c(+)[OTf](-) were determined by single-crystal X-ray analyses. The detailed NMR analysis of the reaction of 2 with aroylacetonitriles revealed that the (alkylideneamido)(nitrile-enolato) complexes trans-[Mo-NCHCH(2)COR)(NCCHCOR)(dppe)(2)] (5) act as the key intermediates for the C=N triple bond fission. and the rate constants for the conversion of the complexes 5 into the nitrido complexes 4 showed good correlation with the Hammett sigma(p) or sigma(a) constants for the aroyl substituents, when positive rho values were obtained (rho(p), 1.42; rho(a), 0.41). A reaction mechanism for the nitrido complex formation is proposed, which includes (1) the substitution of a dinitrogen ligand in 2 with a beta-ketonitrile molecule, (2) the fast protonation of the nitrite ligand by a second beta-ketonitrile molecule leading to the formation of complex 5, (3) the relatively slow proton shift from the a-position of the carbonyl group to the amido carbon in the alkylideneamido ligand to form an enolated imido ligand. and (4) the fast elimination of a vinyl ketone from the imido ligand giving the nitrido complex 4 as the final product.

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Reactions of the dinuclear hydrogensulfido-bridged complexes [Cp*MCl(mu-SH)(2)MClCp*] (M = Rh, Ir) with CuCl2. 2H(2)O lead to formation of Rh4S7 and Ir3CuS6 clusters [(Cp*Rh)(4)(mu(3)-S-2)(2)(mu(4)-S-3)][CuCl2](2) and [(Cp*Ir)(3)(mu(3)-S-2)(3)(CuCl2)][CuCl2] through the oxidative S-S bond formation, the former of which contains a trisulfido ligand of the unprecedented mu(4)-eta(2):eta(1):eta(1):eta(1) coordination mode.

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A novel alpha-tocomonoenol [3,4-dihydro-2,5,7,8-tetramethyl-2-(4,8,12-trimethyl-12-tridecenyl)-2H-1-benzopyran-6-ol] having an unusual methylene unsaturation at the isoprenoid-chain terminus of alpha-tocopherol was isolated from the lipophilic fraction of chum salmon eggs. The structure of this marine-derived tocopherol (MDT) was established by spectral analyses. The peroxyl radical-trapping activities of MDT and alpha-tocopherol were compared in aqueous phosphatidylcholine liposomal suspension and in methanolic solution at 37 degrees C. The antioxidant activity of MDT was found to be identical to that of alpha-tocopherol under the experimental conditions of measurement.

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The molecular structures of [RuH(dppp)(2)](+) (1) and [RuH{OC(CH3)(2)}(dPPe)(2)](+) (2) ions in the PF6- salts were determined by the X-ray crystallography. 1 involves the agostic interaction between the ortho C-H bond of a phenyl group of the dppp ligands and the formally unsaturated Ru center, and takes the cis geometry, where the terminal hydride and the agostic C-H moiety occupy the adjacent sites to each other. 2 adopts a typical octahedral six-coordinate structure with a coordinating acetone molecule trans to the hydride.

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Molybdenum sulfide cluster [Mo3S4(H2O)(9)](4+) and nickel-molybdenum bimetallic sulfide cluster [Mo3NiS4Cl(H2O)(9)](3+) were incorporated into zeolites NaY, HUSY, NaH beta, Na-mordenite (NaMOR), and KL by aqueous ion exchange. EXAFS data revealed that the structure of the molybdenum sulfide cluster remained virtually intact after ion exchange, However, the incomplete cubane-type structure of the cluster might be lost after thermal treatment at 573 K. The structure of the cluster in Mo3S4/NaY and Mo3S4/KL seems to have changed to the MoS2-like structure through the hydrodesulfurization (HDS) reaction, although a considerably high level of dispersion was kept. Mo3S4 cluster catalysts loaded on NaMOR and KL exhibited a higher level of activity for HDS of benzothiophene than Mo3S4 catalysts loaded on the other zeolites. Benzene was formed through acid-catalyzed dealkylation of ethylbenzene, the primary HDS product. Alkylation of benzothiophene with alkenes derived from the cracking of decane as the solvent also occurred, The acidity seems to be produced through the ion exchange and reduction of cationic clusters during activation. Over HUSY- and NaH beta-supported catalysts benzene was the major HDS product, Nickel incorporation into the Mo3S4 zeolite catalysts remarkably enhanced the HDS activity. Introduction of the Mo3NiS4 core into zeolite as a precursor resulted in catalysts with higher HDS activity than that of Mo3S4 core and Ni2+ independently; it is conceivable that the intimate interaction between nickel and molybdenum in the precursor is effective at producing active species. (C) 1999 Academic Press.

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A series of cationic dinuclear hydride complexes with bridging thiolato ligands [Cp*MH(mu-SPri)(2)MCp*] [OTf] (4, M = Ru; 6a, M = Rh; 7a, M = Ir; Cp* = eta(5)-C5Me5, OTf = OSO2CS) were synthesized by treatment of the corresponding chloro complexes [Cp*RuCl(mu-SPri)(2)Ru(OH2)Cp*][OTf] (1) or [Cp*M(mu-Cl)(mu-SPri)(2)MCp*] [OTf] (2, M = Rh; 3, M = Ir) with HSiEt3. The dirhodium and diiridium complexes 6 and 7 have been shown to possess a bridging hydride ligand by crystallographic analysis, while the diruthenium complex 4 is proposed to have a terminal hydride ligand that undergoes facile migration between the two ruthenium centers in solution. Complexes 4, 6a, and 7a reacted with nitrosobenzene to give the paramagnetic dinuclear nitrosobenzene complexes [Cp*M(mu-PhNO)(mu-sPr(i))(2)MCp*](+) (M = Ru, Rh, Ir) along with azoxybenzene. The molecular structures of the three nitrosobenzene complexes have been determined by X-ray diffraction study to reveal that in each case nitrosobenzene acts as a mu-eta(1):eta(1)-N,O ligand. Judging from the molecular structures and the ESR spectra, the unpaired electron is considered to be located mainly on the nitrosobenzene ligand, at least in the diruthenium and dirhodium complexes. On the other hand, complex 2 reacted with nitrosobenzene to give the incomplete cubane-type trinuclear cluster [(Cp"Rh)(3)(mu-Cl)(2)(mu(3)-S)(mu-SPri)](+), whose molecular structure has also been determined crystallographically.

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The tungsten (1-pyridinio)imido complexes [WX(2)(NNC(5)H(4)OMe)(L)(PMe(2)Ph)(2)](+), [WX(2)(NNC(5)H(2)Me(3))(L)(PMe(2)Ph)(2)](+), and [WCl(2){NNC(5)H(2)(COOEt)(2)Ph}(L)(PMe(2)Ph)(2)](+) (X = Cl, Br; L = CO, C(2)H(4), PMe(2)Ph) were synthesized by the reaction of the salts of pyrylium cations with the hydrazido complexes [WX(2)(NNH(2))(L)(PMe(2)Ph)(2)], which were derived from the dinitrogen complex cis-[W(N(2))(2)(PMe(2)Ph)(4)]. The complexes obtained were characterized by spectroscopic measurements as well as crystallographic studies of cis,mer-[WBr(2)(NNC(5)H(4)OMe-4)(PMe(2)Ph)(3)][PF(6)], cis, trans-[WCl(2)(NNC(5)H(4)OMe-4)(CO)(PMe(2)Ph)(2)][ClO(4)], cis, trans- [WCl(2)(NNC(5)H(2)Me(3)-2,4,6)(CO)(PMe(2)Ph)(2)][OTf] (OTf = OSO(2)CF(3)), and cis,trans-[WCl(2)(NNC(5)H(4)OMe-4)(C(2)H(4))(PMe(2)Ph)(2)][ClO(4)], which revealed that the N-N bond distances of these (1-pyridinio)imido complexes are shorter than those of the trialkyl- or unsubstituted hydrazidium complexes so far reported. The (1-pyridinio)imido complexes with a pi-acidic ligand (CO or C(2)H(4)) undervent smooth N-N bond cleavage on reaction with cobaltocene under ambient conditions to liberate the pyridines in moderate to high yields. In some reactions that were conducted in the presence of HNEt(3)-Cl, the corresponding imido (NH) complexes were recovered as the metal products. The (1-pyridinio)imido complexes also reacted with KOH in MeOH to give the pyridines and ammonia in high yields. These reactions provide the first examples of N-N bond cleavage of well-defined hydrazidium complexes and accomplish the synthesis of pyridines from molecular nitrogen under mild conditions.

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Novel (1-pyridinio)imidotitanium(IV) complexes [Cp'TiCl2(NNC5H3R2-2,6)] (3a, Cp' = Cp, R = H; 3b, Cp' = Cp, R = Me; 3c, Cp' = Cp*, R = Me) were synthesized in high yield from [Cp'TiCl3] and [NH2NC5H3R2-2,6][PF6] in the presence of base. Complex 3b could also be prepared from [Cp2TiCl2] and [NH2NC5H3Me2-2,6][PF6] in the presence of 1 equiv of BuLi. Cationic complexes [Cp*Ti(OTf)(NNC5H3Me2-2,6)(bpy)][OTf] (bpy = 2,2'-bipyridine) (4) and [Cp*Ti(NNC5H3Me2-2,6)(terpy)][OTf](2) (terpy = 2,2':6',2 "-terpyridine) (5) were derived from 3c through reaction with AgOTf in the presence of bpy and terpy, respectively. The structures of complexes 3a, 3b, 3c, and 5 were determined by X-ray crystallography. The N-N bond of 3a-c could be cleaved by reduction with sodium amalgam, liberating the corresponding pyridines in high yield, while the N-N bond in 4 and 5 could be reductively cleaved by cobaltocene in moderate yield. The N-N bond in 3a-c could also be cleaved by cobaltocene in the presence of a proton analogue like Me3SiCl.

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Treatment of the pyrrolylimido complexes cis,trons-[WX2(NNCH=CIICHL=CH)(L)(PMe2Ph)(2)] (X = Cl, Br, l; L = PMe2Ph (6), CNBu', CO, PhC CH. PhCHO, Br) with LiAlH4 or KOH produced pyrrole, 1-aminopyrrole, and ammonia, where both the reacnon conditions and the nature of the ligand L showed significant effects on the pyrrole/l-aminopyrrole selectivity. Thus, reduction of cis,trans-[WBr2(NNCH=CHCH=CH)(CNBu'(PMe2Ph)(2)] with LiAlH4 followed by methanolysis gave pyrrole and ammonia in almost quantitative yields. On the other hand, l-aminopyrrole was quantitatively produced from the complexes by the reaction of KOH in alcohol when L = CO, PhC.ECH, or PhCHO. While analogous treatment of 6 with KOH in ethanol afforded both pyrrole and 1-aminopyrrole with low selectivity under N-2 atmosphere, 1-aminopyrrole was produced from 6 in excellent yield under 1 atm of CO. On the contrary, pyrrole and ammonia were selectively formed from the reaction of 6b (X = Br) with KOH/18-crown-6 ether in THF. Replacement of one of the PMe2Ph ligands in the diazoalkane complex cis,mer-WBr2(NN=CMeCH2CH2COMe)(PMe2Ph)(3)] (12) by CO or CNBu' facilitated the cyclization of the diazoalkane ligand to provide the (2,5-dimethylpyrrolyl)imido complexes cis,trans[WBr2(NN=CHCH=CMe)(L)(PMe2Ph)(2)] (L = CO 14 L = CNBu' 15), although complex 12 failed to undergo the ring closure by aqueous HBr. 2,5-Dimethylpyrrole and 1-amino-2,5-dimethylpyrrole were selectively obtained by LiAlH4 reduction of 15 and by treatment of 14 with KOH in EtOH, respectively.

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Novel dinuclear pyridine-l-imine Rh(III) complexes [Cp*Rh(mu(2)-Cl) {mu(2)-NHNC5H4(4-Me)}(2)RhCp*]Cl[PF6](2) (3) and [Cp*Rh(mu(2)-Cl) {mu(2)-NHNC5H3(2-CH2)(6-Me)}RhCl-Cp*][PF6] (4) were synthesized by the reaction of [Cp*RhCl2](2) with [NH2NC5H4(4-Me)][PF6] and [NH2-NC5H3(2,6-Me-2)][PF6], respectively, in the presence of a base. The formation of 4 involves C(sp(3))-H bond activation at the benzylic position of a pyridine-1-imine ligand.

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The hydrazido(2-) complexes [WCl2(NNH2)(L)(PMe2Ph)(2)] (L = PMe2Ph, CO), derived from the dinitrogen complex cis-[W(N-2)(2)(PMe2Ph)(4)] (1), reacted with beta-diketones (RCOCHRCOR3)-C-1-C-2 (R-1 = Me, Bu-t, Ph; R-2 = H, Me; R-3 = Me, Et, Bu-t, Ph) to afford a series of diazoalkane complexes [WCl2(NN=(CRCHRCOR3)-C-1-C-2)(L)(PMe2Ph)(2)]. The detailed structure of cis,mer-[WCl2(NN=CMeCH2COPh)(PMe2Ph)(3)] has been determined by X-ray analyses. These diazoalkane complexes were treated with a KOH/EtOH mixture to produce pyrazoles in moderate yields, whereas the reaction of 1 with a MeCOCH2COPh/KOH/EtOH mixture resulted in the direct formation of 5-methyl-3-phenylpyrazole.

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The thiolate-bridged diruthenium complexes [Cp*RuCl(mu-SR)(2)RuCp*Cl] (R = Me, Et, Pr-n) were found to be effective and highly selective catalysts for the head-to-head Z dimerization of various terminal alkynes including straight-chain aliphatic alkynes and those with functional groups.

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The molybdenum and tungsten dinitrogen-organonitrile complexes trans-[M(N-2)(NCR)(dppe)(2)] (2, M=Mo; 4, M=W; R=Ph, C6H4Me-p, C6H4OMe-p, Me; dppe = Ph2PCH2CH2PPh2) underwent double protonation at the nitrile carbon atom with loss of N-2 and a change in oxidation state to +4 on treatment with hydrochloric acid to afford the cationic imido complexes trans-[MCl(NCH2R) (dppe)(2)](+). The solid-state structure of trans-[WCl(NCH2CH3) (dppe)(2)] [PF6]. CH2Cl2 was determined by single-crystal X-ray analysis. Protonation of complexes 2 by fluoroboric acid or hydrobromic acid also formed the similar imido complexes trans- [MoX(NCH2R) (dppe)(2)](+) (X = F, Br). In contrast, the dinitrogen complex trans-[Mo(N-2)(2)(dppe)(2)] reacted with two equiv. of benzoylacetonitrile, a nitrile with acidic CH hydrogen atoms, to give the nitrido complex trans-[Mo(N) (NCCHCOPh) (dppe)(2)] (12), which was accompanied by evolution of dinitrogen and the formation of 1-phenyl-2-propen-1-one in high yields. For complex 12, the zwitterionic structure, where the anionic enolate ligand PhC(O-)=CHCN coordinates to the cationic Mo(IV) center through its nitrogen atom, was confirmed by spectroscopic measurements and single-crystal X-ray analysis. A unique intermolecular aromatic C-H ... O hydrogen bonding was observed in that crystal structure. Complex 12 is considered to be formed via the cleavage of the C=N triple bond of benzoylacetonitrile on the metal. A reaction mechanism is proposed, which includes the double protonation of the nitrile carbon atom of the ligating benzoylacetonitrile on a low-valent molybdenum center. (C) 1998 Elsevier Science S.A. All rights reserved.

DOI： 10.1016/S0020-1693(98)00060-7

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The triruthenium cluster with bridging ethanethiolato and indenyl ligands [(eta(5)-C(9)H(7))Ru(mu-SEt)](3) (2) was synthesized by heating the mononuclear indenyl complex [(eta(5)-C(9)H(7))Ru(SEt)(PPh(3))(2)] (la) in toluene. Cluster 2 reacted with Mel to afford the S-methylated cluster [(eta(5)-C(9)H(7))(3)Ru(3)(mu-SEt)(2)(mu-SEtMe)]I . CH(2)Cl(2) (4a) with high stereoselectivity through the attack of Mel on the axial SEt group from the equatorial side. The PF(6)(-) salt of the cationic cluster [(eta(5)-C(9)H(7))(3)Ru(mu-SEt)(2)(mu-SEtMe)][PF(6)] was further converted into the cationic carbonyl complex [(eta(5)-C(9)H(7))(2)Ru(2)(mu-SEt)(CO)(4)][PF(6)] (5) by treatment with CO at 50 degrees C. The crystal structures of 4a and 5 were determined by X-ray diffraction study. When a THF solution of 2 was allowed to contact with atmospheric pressure of CO at room temperature, the trinuclear carbonyl cluster [(eta(5)-C(9)H(7))(3)Ru(3)(mu-SEt)(3)(mu-CO)(CO)] (6) and the dinuclear carbonyl complex [(eta(5)-C(9)H(7))Ru(mu-SEt)(CO)](2) (7) were obtained. The structures of 6 and 7 were also crystallographically determined. Furthermore, cluster 2 was oxidized in refluxing CHCl(3) to give [(eta(5)-C(9)H(7))Ru(SEt)Cl](n) (9). The Cp analogue of 2, [CpRu(mu-SEt)](3), failed to react with CO and CHCl(3), and the hapticity change of the indenyl ligand in 2 is considered to be crucial for the initial interaction of 2 with CO and CHCl(3). These reactions provide rare examples of the indenyl ligand effect in a multinuclear complex. (C) 1998 Elsevier Science S.A. All rights reserved.

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Reactions of [Cp*MCl(mu(2)-SH)(2)MCp*Cl] (1, M = Ir; 2, M = Rh; Cp* = eta(5)-C(5)Me(5)) with excess FeCl(2). 4H(2)O in THF grave the paramagnetic trinuclear clusters [(Cp*M)(2)(mu(3)-S)(2)FeCl(2)] (3, M = Ir; 4, M = Rh), which were further converted into the dicationic 78e(-) pentanuclear bow-tie cluster [(Cp*Ir)(2)(mu(3)-S)(2)Fe(mu(3)-S)(2)(IrCp*)(2)](2+) (5) by treatment with NaBPh(4). When complex 1 was allowed to react with CoCl(2) and NiCl(2). 6H(2)O or Ni(cod)(2) (cod cyclooctadiene), the related pentanuclear 79e(-) and 80e(-) bow-tie clusters [(Cp*Ir)(2)(mu(3)-S)(2)M(mu(3)-S)(2)(IrCp*)(2)](2+) (6, M = Co; 7, M = Ni) were obtained directly, respectively. Cyclic voltammograms of 5[BPh(4)](2), 6[BPh(4)](2), and 7[BPh(4)](2) showed two reversible reduction waves at -0.25 to -0.43 V and -1.04 to -1.34 V. In both redox couples, the redox potential was in the order Fe &lt; Co &lt; Ni. One-electron reduction of clusters 5[BPh(4)](2), 6[BPh(4)](2), and 7[BPh(4)](2) with Co(eta(5)-C(5)H(5))(2) gave the corresponding monocationic pentanuclear 79-81e(-) bow-tie clusters [(Cp*Ir)(2)(mu(3)-S)(2)(mu(3)-S)(2)(IrCp*)(2)](+) (8, M = Fe; 9, M = Co; 10, M = Ni). The molecular structures of 3, 4, 5[BPh(4)](2). CH(2)Cl(2), 6[CoCl(3)(NCMe)](2), 7[NiCl(4)]. CH(2)Cl(2), 8[BPh(4)], 9[BPh(4)], and 10[BPh(4)] were unambiguously determined by X-ray diffraction study. The structures of the pentanuclear bow-tie cluster cores remarkably changed stepwise as the core electrons increased from 78 to 81. Two of the M-Ir (M = Fe, Co) bonds in the 79e(-) clusters 6 and 8 show significant elongation in comparison with the Fe-Ir bonds in the 78e- cluster 5. Two different types of the bow-tie structures were observed for the 80e(-) clusters 7 and 9. Cluster 7 has a Z-shaped metal core with only two Ni-Ir bonds, while in cluster 9, the six metal-metal bonds in the bow-tie structure are retained with slight elongation of the Co-Ir bonds in comparison with the corresponding dication 6. The 81e(-) cluster 10 has two normal Ni-Ir bonds and one long Ni-Lr bonding interaction with the fourth nonbonding Ni-Ir contact. This structural variation is interpreted in terms of the total electron counts and molecular orbital calculations of the clusters.

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The dinitrogen complex cis-[W(N-2)(2)(PMe2Ph)(4)] reacted with Ga2Cl4 or GaX3 (X = Cl, Br) to form tetranuclear tungsten-gallium complexes with mu(3)-eta(1):eta(1):eta(1)-N-2 ligands, trans, trans- [{WX(PMe2Ph)(4)(mu(3)-N-2)}(2)(GaX2)(2)] (3). The molecular structure of complex 3a (X = Cl) has been determined by X-ray diffraction study.

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Novel Ru(II) and Ru(III) complexes having TPA (tris(2-pyridylmethyl)amine, L1) and 5-Me-3-TPA (tris(5-methyl-2-pyridylmethyl)amine, L2) were prepared to establish their synthetic routes and to elucidate coordination geometry and interactions between tightly bound tripodal tetradentate ligands and (RuRuIII)-Ru-II/ centers. They include mononuclear Ru(II) complexes [RuCl(DMSO)(L)]ClO4 (1 (L1), 2 (L2)), dinuclear bis-mu-chloro Ru(LI) complexes [RuCl(L)](2)(ClO4)(2) (3 (L1), 4 (L2)), and mononuclear Ru(III) complexes [RuCl2(L)]ClO4 (5 (L1), 6 (L2)). They were characterized by X-ray crystallography (for 2, 3, and 5), H-1 NMR spectroscopy, and cyclic voltammetry. For compound 2, the crystal structure was determined to possess S-bound DMSO ligand which was trans to pyridine and Cl- trans to the tertiary amino group of L2, and this isomer was obtained exclusively. Complex 1 was also isolated as a single isomer. Complex 3 was revealed to be a dinuclear bis-mu-chloro Ru(II) species with the center of symmetry midway between two Cl-. H-1 NMR spectra of Ru(II) complexes 1-4, the molecular structure of 2, and comparison of the molecular structure of 3 with 5 suggest that the interaction between the Ru(II) center, pyridyl moieties, and the DMSO ligand is strengthened by pi-back-bonding from the Ru(II) center to the ligands in addition to sigma-bonding of the tertiary amino group. Electrochemical measurements on 1-6 in CH3CN revealed that the methyl groups on pyridyl rings exert electron-donating effects onto the Ru centers to lower each redox process and such effect strengthens the Ru-S bonding in 2 compared with that in 1, accommodating ct-back-bonding from Ru(II) center to other pi-acceptors such as DMSO in 2 enough to prevent isomerization of DMSO binding mode. The dinuclear complexes 3 and 4 showed relatively large comproportionation constants, which suggest mixed-valent (RuRuIII)-Ru-II states would be stabilized.

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The triangular heterobimetallic sulfide cluster [(Cp*Ir)(2)(mu(3)-S)(2)PdCl2] prepared from [PdCl2(cod)] and [Cp*IrCl(mu-SH)(2)IrCp*Cl] was found to catalyze the addition of alcohols to alkynes to give the corresponding ketals. In particular, internal 1-aryl-1-alkynes were transformed into the corresponding 2,2-dialkoxy-1-arylalkanes with high regioselectivity. The analogous Ir2PtS2 cluster proved to be much less selective.

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The anionic tungsten dinitrogen complex trans-[NBu4][W(NCS)(N-2)(dppe)(2)] reacted with primary and secondary boranes to give the corresponding boryldiazenido complexes, among which trans-[W(NCS)(N=NBHCMe2CHMe2)(dPPe)(2)] was structurally determined. A related boryldiazenido complex was also obtained by the reaction of trans-[W(N-2)(2)(dppe)(2)] with 9-borabicyclo[3.3.1]nonyl trifluoromethanesulfonate. These reactions provide the first examples of boration of coordinated dinitrogen.

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The reaction of [Cp*MCl(mu(2)-Cl)(2)MCp*Cl] (M = Ir, Rh; Cp* = eta(5)-C5Me5) with excess H2S gas for 5 min afforded the doubly bridged hydrosulfido complexes [Cp*MCl(mu(2)-SH)(2)MCp*Cl] (3: M = Ir, 4: M = Rh) which were further transformed into the triply bridged cationic hydrosulfido complexes [Cp*M(mu(2)-SH)(3)MCp*]Cl(5 . Cl:M = Ir, 6 . Cl: M = Rh) by continuous stirring under H2S. The molecular structures of 3, 4, 5 .[BPh4] and 6 . Cl . C6H6 were determined by X-ray analyses. The SH ligands in complexes 3 and 4 take anti configuration in the solid state, whilst these complexes exist as mixtures of the syn and anti isomers in solution. Strong hydrogen bonds between the Cl anion and two of the SH ligands were found in 5 . Cl and 6 . Cl, and were maintained in CDCl3 solution. When complexes 3 and 4 were treated with NEt3 at room temperature, the cubane-type sulfide clusters [(Cp*M)(4)(mu(3)-S)(4)] (M=Ir, Rh) were produced in high yields. In the reaction of 3, an intermediary complex, most probably [Cp*Ir(mu(2)-S)(2)IrCp*], was detected by H-1 NMR. (C) 1998 Elsevier Science S.A.

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The molybdenum sulfide cluster [Mo3S4(H2O)(9)](4+) (1) and the nickel-molybdenum bimetallic sulfide cluster [Mo3NiS4Cl(H(2)0)(9)](3+) (2) were incorporated into zeolites NaY, HUSY, KL, NaMOR and NaH beta by aqueous ion-exchange, The catalysts supported on KL and NaMOR exhibited a higher activity for hydrodesulfurization (HDS) of benzothiophene than catalysts supported on other zeolites. Nickel incorporation into Mo/zeolite catalysts enhanced the HDS activity remarkably. ?he catalysts prepared by ion-exchanging zeolites with 2 were more active in the HDS reaction than the catalysts prepared by ion-exchanging 1/zeolite with nickel nitrate solution; the presence of the Mo-S-Ni linkage in 2 will be effective for producing active HDS species. (C) 1997 Elsevier Science B.V.

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The cationic diruthenium complexes with a terminal vinylidene ligand [Cp*RuCl(mu(2)-SPri)(2)-Ru(=C=CHR)Cp*][OTf] (3a, R = COOMe; 3b, R = COMe; 3c, R = H; Cp* = eta(5)-C5Me5, OTf = OSO2CF3) were obtained in high yields by the reaction of [Cp*RuCl(mu(2)-SPri)(2)Ru(OH2)Cp*][OTf] with HC=CR. Hydration of 3a and 3b gave the carbonyl complex [Cp*RuCl(mu(2)-SPri)(2)Ru(CO)Cp*][OTf] and CH3R in almost quantitative yields, while the reaction of 3c with water gave the mu(2)-acetyl complex [Cp*RuCl(mu(2)-SPri)(2){mu(2)-C(=O)Me}RuCp*][OTf] (5). A reaction mechanism for the former reactions is proposed, which includes hydration of the vinylidene ligands to form the mu(2)-beta-ketoacetyl complexes with a six-membered dimetallacyclic structure [Cp*Ru(mu(2)-SPri)(2)(eta(1):eta(1)-mu(2)-mu(2)-COCH2COR')RuCp*](+) (R' = OMe, Me) and the following decarbonylation reaction of the mu(2)-COCH2COR' ligand on the bimetallic center to produce the carbonyl complex and CH3COR' via the enolato-carbonyl complexes [Cp*Ru(CO)(mu(2)-SPri)(2)Ru(OCR'=CH2)Cp*](+). In accordance with this mechanism, the reaction of 3a with MeOH afforded [Cp*Ru(mu(2)-SPri)(2){eta(1):eta(1)-mu(2)-C(OMe)=CHCOOMe}RuCp][OTf] (7). Complexes 3a and 3b reacted with p-tolylacetylene to form the dinuclear metallacyclic complexes 9a and 9b [Cp*Ru(mu(2)-SPri)(2){eta(1):eta(1)-mu(2)-C(Tol)=CCCH=C(R')O}RuCp][OTf] (9a, R' = OMe; 9b, R' = Me), respectively. The structures of 3b, 5, 7, and 9a have been determined by X-ray crystallography.

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The hydrosulfido-bridged diiridium and dirhodium complexes [Cp*MCl(mu(2)-SH)(2)MCp*Cl] (3, M = Ir; 4, M = Rh; Cp* = eta(5)-C(5)Me(5)) were obtained by the reaction of [CP*MCl(mu(2)-Cl)(2)MCp*Cl] (M = Ir, Rh) with excess H2S gas. Treatment of 3 and 4 with NEt(3) gave the cuboidal sulfide clusters [(Cp*M)(4)(mu(3)-S)(4)] (M = Ir, Rh), while their reaction with [RhCl(cod)](2) (cod = 1,5-cyclooctadiene) or [Pd(PPh(3))(4)] afforded the cationic triangular sulfide clusters [(Cp*M)(2)Rh(mu(3)-S)(2)(cod)](+) (M = Ir, Rh) or [(Cp*Ir)(2)Pd(mu(3)-S)(2)Cl(PPh(3))](+), respectively.

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Acid-catalyzed reactions of the hydrazido(2-) complexes cis,mer-[WX(2)(NNH2)(PMe(2)Ph)(3)] (X=Cl, Br) with phthalaldehyde gave the (phthalimidin-2-yl)imido complexes cis,mer-[WX(2)(NNCH2C6H4CO)(PMe(2)Ph)(3)], via the condensation of the terminal NH2 group with one of the formyl groups and the following cyclization to form a phthalimidine ring. Crystal structure of the chloro complex 3a was unambiguously determined by X-ray analysis. Reaction of 3a with HBr liberated the (phthalimidin-2-yl)imido ligand as 2-aminophthalimidine in moderate yield, while treatment of 3a with KOH in THF selectively cleaved the N-N bond to give phthalimidine. A similar condensation of the hydrazido(2-) complex trans-[WF(NNH2)(dppe)(2)](+) (8a(+); dppe=Ph(2)PCH(2)CH(2)PPh(2)) with phthalaldehyde resulted in the formation of the diazoalkane complex trans-[WF(NN=CHC6H4CHO)(dppe)(2)](+). However, further treatment of the latter complex with AlCl3 afforded the corresponding (phthalimidin-2-yl)imido complex trans-[WF(NNCH2C6H4CO)(dppe)(2)](+). When 8a(+) and its molybdenum analogue were reacted with 2,5-dimethoxy-2,5-dihydrofuran in the presence of a catalytic amount of acid, trans-[M(NNCH=CHCH2CO)(dppe)(2)](+) (11(+); M=Mo, W) was formed as the kinetic product, which gradually isomerized to the thermodynamically more stable compound trans-[MF(NNCH2CH=CHCO)(dppe)(2)](+) (12(+)). Both 11(+) and 12(+) (M=W) were crystallographically characterized, and the mechanism for the isomerization of 11(+) to 12(+) was proposed based on the results of the H-1 NMR measurements.

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The incomplete cubane-type cluster, [Mo3S4(H2O)(9)](4+), and the complete cubane-type clusters, [Mo3NiS4Cl(H2O)(9)](3+) and [Mo3PdS4Cl(H2O)(9)](3+), have been incorporated into zeolites NaY, HUSY, KL, NaMOR and NaH beta by ion exchange. The UV-visible spectra and EXAFS analysis data exhibited that the structure of the molybdenum cluster was maintained after ion exchange but changed after thermal treatment. Destruction of zeolite structure was hardly observed from XRD analyses. These molybdenum-zeolite catalysts, molybdenum-nickel catalysts in particular, were highly selective for C-2 formation from CO-H-2.

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Reaction of [{Ru(η5-C5Me5)(μ3-Cl)} 4] with 2 equivalents of REER (E = S, Se or Te
R = ferrocenyl) gave novel ferrocenylchalcogenolate-bridged diruthenium complexes [{Ru(η5-C5Me5)Cl(μ-ER)}2] in good yields. Reduction of these by sodium amalgam in the presence of buta-1,3-diene afforded [{Ru(η5-C5Me5)(μ-ER)} 2-(μ-s-trans-η2:η2′-CH 2=CHCH=CH2)], whereas treatment with AgOSO2CF3 produced the co-ordinatively unsaturated complexes [Cl(η5-C5Me5)Ru(μ-ER) 2Ru(η5-C5Me5)][OSO 2CF3]. The structures of five of the complexes have been defined by X-ray crystallography. © Copyright 1996 by the Royal Society of Chemistry.

DOI： 10.1039/DT9960004307

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Reaction of acetylacetone (Hacac) with aldehyde (RCHO; R = p-MeOC(6)H(4), p-ClC6H4 or Ph) in 2: 1 mol ratio resulted in the formation of new triketones (HL(2)), which were previously characterized as bis(beta-diketones) of the type [(MeCO)(2)CHCHRCH(COMe)(2)](H(2)L(1)). Mixed-ligand copper(II) complexes with N,N,N',N'-tetramethylethane-1,2-diamine (tmen) and the beta-diketonate moiety of these triketones, [CuCl(L(2))(tmen)], were synthesized and their solvatochromic properties in organic solvents (due to the acceptor properties of the solvent) investigated. The colour of these five-co-ordinated complexes in the solid state gradually changes from green in [CuCl(L(2))(tmen)] through bluish green, [CuCl(L(2))(tmen)]. CH2Cl2, to blue, [CuCl(L(2))(tmen)]. MeOH . CH2Cl2. Crystallographic studies showed that this phenomenon arises from an intermolecular hydrogen bond between the co-ordinated chloride of one complex and the OH group of a triketonate ligand of an adjacent complex and/or cocrystallized MeOH molecule.

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Zeolites NaY, HUSY and KL were ion-exchanged with a cationic molybdenum sulfide cluster [Mo3S4(H2O)(9)](4+) with incomplete cubane-type structure and a cationic nickel-molybdenum mixed sulfide cluster [Mo3NiS4Cl(H2O)(9)](3+) with complete cubane-type structure. The UV-visible spectra and EXAFS analysis data exhibited that the structure of the molybdenum cluster was maintained after ion exchange. These zeolite catalysts showed activity for benzothiophene hydrodesulfurization; especially, involvement of Ni resulted in great enhancement of the hydrodesulfurization activity.

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Direct synthesis of organo-nitrogen compounds from molecular nitrogen is a challenging subject in the chemistry of nitrogen fixation. Toward this direction, we have long been investigating novel chemical transformations of coordinated dinitrogen. Described herein are our recent results on (1) synthesis of nitrogen-heterocycles from molecular nitrogen via condensation reactions of hydrazido complexes with dialdehydes or their equivalents, (2) bimetallic arylation of molecular nitrogen by using reactions of anionic dinitrogen complexes with eta(6)-fluoroarene complexes, and (3) catalytic silylation of molecular nitrogen.

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A series of thiolate-bridged dinuclear ruthenium complexes containing two electron-deficient olefinic ligands [Cp*Ru(mu-SR)(2)(eta(2)-C(2)H(3)R')(2)RuCp*] (R = Pr-i, Et, 2,6-C(6)H(3)Me(2) or 2,4,6-C(6)H(2)Me(3); R' = CN, COOMe or CHO) have been synthesized from Ru(II)-Ru(II), Ru(II)-Ru(III) and/or Ru(III)-Ru(III) precursors, three of which have been characterized by X-ray structural analysis.

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Hydrazido(2-) complexes trans-[MX(NNH2)(dppe)(2)](+) (M = Mo, W; X = F, Cl; dppe = Ph(2)PCH(2)CH(2)PPh(2)) and cis,mer-[WX(2)(NNH2)(PMe(2)Ph)(3)] (X = Cl, Br), which are readily derived from trans-[M(N-2)(2)(dppe)(2)] (1) and cis-[W(N-2)(2)(PMe(2)Ph)(4)] by protonation, condensed with 2,5-dimethoxytetrahydrofuran to afford pyrrolylimido complexes of the type trans-[MX(NNCH=CHCH=CH)(dppe)(2)](+) (3(+)) and cis,mer-[WX(2)(NNCH=CHCH=CH)(PMe(2)Ph)(3)] (6), respectively. Their structures were characterized spectroscopically and further confirmed by X-ray diffraction study. Electrophilic substitution reactions at the pyrrole ring in complexes 3(+) occurred selectively at the beta-position to give the corresponding beta-substituted pyrrolylimido complexes trans- [MX(NNCH=C(E)CH=CH)(dppe)(2)](+) (E Br, CN, SO3-, COR), although only chlorination of 3(+) with N-chlorosuccinimide in THF took place predominantly at the a-position. This beta-regioselectivity is in sharp contrast to the a-regioselectivity of free pyrrole and is probably caused by the steric effect of the dppe ligands. Complexes 3(+) were readily reduced under ambient conditions with LiAlH4 to liberate pyrrole and N-aminopyrrole in high yields. Further, the tetrahydrido complexes [MH(4)(dppe)(2)], which can be converted back into the original dinitrogen complexes 1, were recovered in moderate yields after the reduction. This accomplishes the synthetic cycle for pyrrole and N-aminopyrrole starting from the dinitrogen complexes 1. beta-Heptylpyrrole was also prepared by starting from 3c(+) (M = W, X = Cl) by the beta-selective heptanoylation followed by the reduction with LiAlH4. On the other hand, reduction of 6b (X = Br) with LiAlH4 predominantly produced pyrrole, whereas treatment of 6b with KOH/EtOH liberated N-aminopyrrole in a high yield.

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The incomplete cubane-type cluster, [Mo3S4(H2O)(9)](4+), and the complete cubane-type cluster, [Mo3NiS4(H2O)(9)CI](3+), are incorporated into 12-membered ring zeolites by ion exchange, leading to catalysts which are highly selective for C-2 formation from CO-H-2.

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The complex [Pd(PPh(3))(4)] showed good catalytic activity for the formation of aroylcobalt complexes [Co(OCR)(CO)(3)(PPh(3))] from RI (R = aryl), K[Co(CO)(4)] and PPh(3). Attempts to isolate an intermediate Pd-Co complex in this catalytic reaction were unsuccessful, however a series of heterodinuclear complexes [(Ph(3)P)(OC)RPtCo(CO)(3)(PPh(3))] (R = Ph 1a, C(6)H(4)Me-4 1b or Me 1c), [(Me(3)P)(2)(PhCO)PdCo(CO)(4)] 2 and [(Me(3)P)(2)PhPtCo(CO)(4)] 3 have been prepared from reactions of [MR(O3SCF3)(PR'(3))(2)] (M = Pt or Pd, R' = Me or Ph) with K[Co(CO)(4)] as model intermediate complexes. Prior to the formation of complex 1, transient formation of [(Ph(3)P)(2)RPtCo(CO)(4)] was confirmed by P-31 NMR spectroscopy Of the reaction solution. The reaction of [PtPh(O3SCF3)(PMe(3))(2)] with K[Co(CO)(4)] led to the isolation of the corresponding Pt-Co complex 3, while the palladium analogue resulted in the formation of the CO insertion product 2. Crystal structures of compounds 1a, 1c, 2 and 3 were determined by X-ray diffraction analyses. Addition of ligands L such as CO, Bu(t)NC and PMe(3) to 3 in tetrahydrofuran induced heterolytic cleavage of the Pt-Co bond to form [PtPh(PMe(3))(2)L][Co(CO)(4)]. Thermolysis of complexes 1b and 1c under CO at 50 degrees C resulted in reductive elimination of Co(OCC(6)H(4)Me-4)(CO)(3)(PPh(3)) and Co(OCMe)(CO)(3)(PPh(3)), respectively, from the platinum centre. This strongly suggests the involvement of this type of heterodinuclear Pd-Co complex in the catalytic formation of aroylcobalt complexes.

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Reaction of [NBu(4)][W(CN)(N-2)(dppe)(2)] with [RuCp(eta(6)-p-FC(6)H(4)R)][PF6] gave novel mu-aryl isocyanide complexes [WF{CN(eta(5)-p-C(6)H(4)R)RuCp}(dppe)(2)] (3) through the arylation of the CN ligand concurrent with the loss of the dinitrogen ligand. The X-ray crystallographic study of 3a (R = H) revealed the unusual eta(1):eta(5)-mu(2)-coordination of the phenyl isocyanide behaving as an iminocarbyne-cyclohexadienyl ligand.

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By adding lanthanoid ion (Ln) to a solution of non-charged iron(II) complex, [Fe(CN)(2)(phen)(2)], the blue shift in MLCT band of the Fe(II) complex was observed in ethanol, but was not in DMSO, The extent of the band shift depends on the lanthanoid ion size, which is explained by means of Fe-C=N-Ln interaction. In DMSO, however, the lanthanoid ion is solvated too strongly to form the Fe-C=N-Ln bridging. The existence of the bridging mode was confirmed by means of the crystal analysis for a Fe2Yb2 tetranuclear complex.

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A novel catecholato complex, Nb-V(tpp)(cat)(Hcat), where cat and Heat are two distinct catechol ligands (a bidentate catecholate dianion and a monodentate catecholate monoanion, respectively) and tpp is 5,10,15,20-tetraphenylporphyrin dianion, has been isolated in the reaction of NBV(tpp)(O)(AcO) with catechol, where AcO is an acetato ligand. Its molecular structure has been determined by X-ray crystallography. Crystal data: monoclinic, space group P2(1)/c, Z = 4, a = 14.592(3) Angstrom, b = 23.46(1) Angstrom, c = 14.415(4) Angstrom, beta = 100.95(2)degrees, R = 0.079. The molecular structure was confirmed to have no oxo ligand, and in this respect it is unique among the niobium(V) porphyrins. The bidentate and monodentate ligands are located on the same side of the porphyrin ring. The heptacoordinate niobium atom is bonded to the four gyrrole nitrogen atoms and to three oxygen atoms in the catechols. The niobium atom is displaced by 1.02 Angstrom from the mean plane of the four nitrogen atoms. The structure of the complex in solution and the mechanism of the Nb = O cleavage were investigated by means of H-1-NMR spectroscopy. The bidentate catechol is oriented in C-s symmetry with respect to the porphyrin plane, and the monodentate catechol is located perpendicularly to both the bidentate catechol and the porphyrin plane. Two intermediates with the bidentate catechol were observed after addition of 2 equiv of catechol to Nb(tmp)(O)(AcO) at -30 degrees C, where tmp denotes the 5, 10, 15, 20-tetramesitylporphyrin dianion. These intermediates were determined to be Nb(tmp)(cat)(OH) and Nb(tmp)(cat)(AcO). Thus, the Nb = O bond of Nb(tmp)(O)(AcO) was easily cleaved to create the two intermediates. We propose a unique route to the Nb = O cleavage that involves an intramolecular electron transfer from the catechol ligand coordinated at the first stage through a ligand exchange with AcO. Both protonation and electron transfer to the Nb = O moiety play important roles in the Nb = O cleavage.

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A cationic thiolate-bridged diruthenium complex [Cp(*)RuCl-(mu(2)-SPri)(2)RuCp(*)][OTf] (Cp* = eta(5)-C(5)Me(5), OTf = OSO2CF3) was found to be an efficient catalyst for the reaction of aromatic aldehydes with hydrosilanes in acetonitrile to give 1,2-diaryl-1,2-disiloxyethanes as the major products.

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Reaction of two acetylacetones with p-anisaldehyde resulted in a new beta-diketonate ligand which can form a mixed ligand Cu(II) complex with an N-alkylated ethylenediamine. The X-ray structure of the complex was determined and its chromotropic property in solution characterized.

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zThe mixed-metal sulfide cubane-type cluster complex [PdMo3S4(tacn)(3)Cl][PF6](3) (1; tacn = 1,4,7-triazacyclononane) was found to be a highly efficient and selective catalyst for the addition of carboxylic acids to acetylenes with electron-withdrawing groups. The corresponding trans addition products were exclusively obtained in good yields under mild reaction conditions in the presence of a catalytic amount of triethylamine.

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Treatment of [Cp(*)RuCl(mu(2)-SPri)(2)RuCp(*)][OTf] (1; CP* = eta(5)-C(5)Me(5), OTf = OSO2CF3) with HC=CFc (Fc = ferrocenyl) at room temperature afforded the dinuclear butenynyl complex [Cp(*)Ru{eta(1):eta(2)-mu(2)-C(=CHFc)C=CFc}(mu(2)-SPri)(2)RuCp(*)][OTf] (4a), the molecular structure of which has been. determined by X-ray diffraction analysis of the corresponding BPh(4)(-) salt 4b. Complex 4a is an effective catalyst for di- and trimerization of the alkyne to yield the head-to-head Z dimer CHFc=CHC=CFc (5) and the linear Z,Z trimer CHFc=CHCFc=CHC=CFc (6).

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The PdCl2(PPh(3))(2)-Ru-3(CO)(12) or PdCl2(PPh(3))(2)-Co-2(CO)(8) bimetallic catalyst has been found to be effective for carbonylation of aryl iodides and HSiEt(3) to give benzyl silyl ether as the major product, although neither PdCl2(PPh(3))(2), Ru-3(CO)(12), nor Co-2(CO)(8) alone had any appreciable catalytic activity. Addition of NEt(3) to the Pd-Co mixed-metal-catalyzed carbonylation reaction remarkably changed the selectivity of the products, and 1,2-diaryl-1,2-disiloxyethane was obtained as the major product. Studies on the hydrosilylation of 4-TolCHO with HSiEt(3) under CO revealed that the formation of benzyl silyl ether in the former reaction may proceed through the formylation of aryl iodide followed by hydrosilylation of the resulting aldehyde. In contrast, the aldehyde was not included as an intermediate in the formation of 1,2-diaryl-1,2-disiloxyethane in the latter reaction. An aroylcobalt complex ArCOCo(CO)(3)(PPh(3)) was suggested as an intermediate for the 1,2-diaryl-1,2-disiloxyethane production based on the following observations: (1) the aroylcobalt complex ArCOCo(CO)(3-)(PPh(3)) can be produced from aryl iodide, [Co(CO)(4)](-), and PPh(3) with a Pd(O) catalyst; (2) hydrosilylation of the aroylcobalt complex ArCOCo(CO)(3)(PPh(3)) under 50 atm of CO pressure produced 1,2-diaryl-1,2-disiloxyethane as the major product. The detailed mechanisms are proposed for the catalytic carbonylations of aryl iodides with HSiEt(3) by using the bimetallic catalysts.

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Addition of methyl formate to alpha,beta-unsaturated methyl esters was catalyzed by Ru-3(CO)(12) to form substituted dimethyl malonates concurrent with small amounts of succinates. A reaction mechanism is proposed which includes an alpha-methoxycarbonylalkyl complex as the major key intermediate.

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The anionic dinitrogen complex [NBu(4)][W(NCS)(N-2)(dppe)(2)] (6, dppe = Ph(2)PCH(2)CH(2)PPh(2)) smoothly reacted with eta(6)-fluoroarene complexes such as [Cr(eta(6)-P-FC(6)H(4)R)(CO)(3)] (3a, R = COOMe) and [RuCp(eta(6)-FC(6)H(4)R)][PF6] (5, Cp = eta(5)-C5H5, R = H, Me, OMe, COOMe) in THF under mild conditions (0 degrees C to room temperature) to give novel mu-aryldiazenido complexes [W(NCS){N=N[(eta(6)-p-C(6)H(4)COOMe)Cr(CO)(3)]}(dppe)(2)] (7) and [W(NCS){N=N[(eta(6)-p-C(6)H(4)R)-RuCp]}(dppe)(2)][PF6] (10), respectively. mu-Aryldiazenido complexes 7 and [WF{N=N[(eta(6)-p-C(6)H(4)R)Cr(CO)(3)]}(dppe)(2)] (8a, R = COOMe) were also obtained by irradiation of a THF solution of [W(N-2)(2)(dppe)(2)] and 3a in the presence of NBu(4)X(X = SCN or F). The structures of these complexes were fully characterized by spectroscopic and X-ray diffraction analysis. The long N=N bond lengths (1.314(5) Angstrom for 7, 1.33(1) Angstrom for 8a, 1.28(1) Angstrom for 10a (R = H)) and the short N-C bond lengths (1.366(6) Angstrom for 7, 1.30(2) Angstrom for 8a, and 1.40(2) Angstrom for 10a) indicate delocalization of the N=N pi-electrons over the aromatic ring. The reaction was suggested to proceed by the direct nucleophilic aromatic substitution mechanism, rather than the radical mechanism so far reported for alkylation reactions of coordinated dinitrogen. Furthermore, reactions of the diazenido complex [WF(NNH)(dppe)(2)] (12) with fluoroarene complexes 3 (R = COOMe, H) and [FeCp(eta(6)-FC(6)H(4)R)][PF6] (4; R = H, Me) also provide a route to mu-aryldiazenido complexes such as 8 and [WF{N=N[(eta(6)-p-C(6)H(4)R)FeCp]}(dppe)(2)]- [PF6] (13), respectively. Crystallographic data for 7.CH2Cl2: formula C65H57N3O5SP4Cl2-CrW, space group P2(1)/n (monoclinic); a = 24.135(3) Angstrom, b = 20.967(5) Angstrom, c = 12.273(5) Angstrom, beta = 90.06(4)degrees, V = 6210(5) Angstrom(3), Z = 4, R = 0.034, R(w) = 0.029. 8a.2THF: formula C71H71N2O7-FP4CrW, space group P2(1)/a (monoclinic); a = 23.110(5) Angstrom, b = 23.402(7) Angstrom, c 12.046(3) Angstrom, beta = 93.89(2)degrees, V= 6500(3) Angstrom(3), Z = 4, R = 0.056, R(w) = 0.066. 10a.CH2Cl2: formula C65H60N3F6-SP5Cl2RuW, space group P ($) over bar 1 (triclinic); a = 12.630(2) Angstrom, b = 23.648(3) Angstrom, c = 11.507(3) Angstrom, alpha = 103.11(1)degrees, beta = 102.77(1)degrees, gamma = 83.44(1)degrees, V = 3257.1(9) Angstrom(3), Z = 2, R = 0.062, R(w) = 0.054. 13b.Me(2)CO (R = Me): formula C67H66N2OF7P5FeW, space group C2/e (monoclinic); a = 38.090(9) Angstrom, b = 18.507(4) Angstrom, c 18.359(3) Angstrom, beta = 91.25(2)degrees, V = 12939(5) Angstrom(3), Z = 8, R = 0.061, R(w) = 0.071.

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An incomplete cubane-type cluster [Mo3S4(H2O)(9)]Cl-4 (1) reacted with Pd black in aqueous HCl to give a mixed-metal cubane-type cluster [PdMo3S4(H2O)(9)Cl]Cl-3 (2). Treatment of 2 with 3.3 equiv of 1,4,7-triazacyclononane (tacn) afforded a well-defined single cubane-type cluster [PdMo3S4(tacn)(3)Cl]Cl-3 (3), while an anion metathesis of 2 by 4-toluenesulfonate (TsO) resulted in the formation of a double cubane-type cluster [Pd2Mo6S8(H2O)(18)] (OTs)(8) (4). Detailed structures of both 3 and 4 have been determined by X-ray crystallography. Crystal data for 3.4H(2)O: orthorhombic, space group P2(1)2(1)2(1), a = 17.549(3) Angstrom, b = 20.032(4) Angstrom, c = 10.256(2) Angstrom, V = 3605 Angstrom(3), Z = 4, and R (R(w)) = 0.051 (0.062) for 4014 reflections. For 4.24H(2)O: triclinic, space group P1, a = 15.799(4) Angstrom, b = 18.079(6) Angstrom, c = 11.873(1) Angstrom, alpha = 108.75(2)degrees, beta = 108.73(1)degrees, gamma = 70.87(3)degrees, V = 2944 Angstrom(3), Z = 1, R (R(w)) = 0.028 (0.036) for 10 089 reflections. Cluster 3 was converted into a series of single cubane-type clusters [PdMo3S4(tacn)(3)(L)](4+) containing alkenes, CO, and (t)BuNC coordinated to the tetrahedral Pd site, by the initial anion exchange forming [PdMo3S4(tacn)(3)Cl]X(3) (8a, X = ClO4; 8b, X = BF4; 8c, X = PF6) followed by treatment with these molecules. The alkene cluster [PdMo3S4(tacn)(3)(cis-HOCH2CH=CHCH2OH)](ClO4)(4) (5a') and the carbonyl cluster [PdMo3S4(tacn)(3)(CO)]Cl(ClO4)(3) (6a) have been fully characterized by X-ray analyses. Crystal data for 5a'.2H(2)O: monoclinic, space group P2(1)/m, a = 12.314(1) Angstrom, b = 12.732(2) Angstrom, c = 15.736(2) Angstrom, beta = 94.01(1)degrees, V = 2461 Angstrom(3), Z = 2, R (R(w)) = 0.068 (0.081) for 2743 reflections. For 6a.3H(2)O: orthorhombic, space group Pbca, a = 15.485(13) Angstrom, b = 23.900(6) Angstrom, c = 23.326(7) Angstrom, V = 8633 Angstrom(3), Z = 8, and R (R(w)) = 0.061 (0.069) for 7761 reflections. Interestingly, cluster 8c catalyzes the reaction of a series of alkynic acid esters R(2)C-CCOOR(1) with alcohols R(3)OH to give the trans addition products (Z)-(R(3)O)R(2)C=CHCOOR(1) (R(1) = Me, Et, (t)Bu, Ph, R(2) = H, R(3) = Me; R(1) = R(3) = Me, R(2) = COOMe, Me; R(1) = Ph, R(2) = Et, R(3) = Me; R(1) = Me, R(2) = H, R(3) = Et, PhCH(2)) with quite high selectivity under mild conditions with retention of the cluster core.

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A series of novel C-60 rhodium complexes [Rh(acac)(L)2(eta(2)-C60)] (L = pyridine, 4-methylpyridine, 3,5-dimethylpyridine) were prepared by the reaction of [Rh(acac)(C2H4)2] with C-60 followed by treatment with pyridine or its derivatives. The molecular structure of [Rh(acac)(3,5-,Me(2)py)(2)(eta(2)-C-60)].C6H6 was determined by the X-ray crystallographic analysis.

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Anion complex [Co(CO)(4)](-) reacted with iodoarenes to form aroylcobalt complexes in the presence of a palladium catalyst and excess PPh(3). As models of the intermediate of this reaction, Pt-Co and Pd-Co dinuclear complexes were synthesized from reactions of [Co(CO)(4)](-) with Pt(Ar)(OTf)(PPh(3))(2) and Pd(Ar)(OTf)(PMe(3))(2), respectively, and their crystal structures were determined by X-ray analysis.

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Beta-Alkylation of alpha,beta-unsaturated diazoalkane complexes [MF(NN=CHCR=CHR1)(dpe)2]X (1,M = W, Mo; X = BF4, PF6; dpe = Ph2PCH2CH2PPh2) by lithium dimethyl- or diphenylcuprates LiCuR22 leads to the formation of the alkenyldiazenido complexes [MF(N=NCH=CRCHR1R2)(dpe)2] (2). Protonation of 2 at the alpha-carbon of the alkenyldiazenido ligands produced beta-monoalkylated diazoalkane complexes in moderate to high yields. Complexes 2 also reacted with alkyl halides or isocyanates to give the corresponding alpha-alkylated or acylated diazoalkane complexes, respectively, in good yields, and these reactions provide a method for the alpha,beta-difunctionalization of 1. Hydrolysis of the diazoalkane complexes obtained by the above method in alkaline THF-H2O under air yielded the corresponding aldehydes. Reaction of alpha,beta-acetylenic diazoalkane complexes [WF(NN=CHC=CR1)(dpe)2]X (6) with LiCuR22 followed by protonation or treatment with I2 gave [WF(NN=CHCH=CR1R2)(dpe)2]X or [WF(NN=CHCI=CR1R2)(dpe)2]X, respectively.

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Phenyl acetates were selectively obtained in good yields by cyclocarbonylation of 2,4-pentadienyl acetates in the presence of NEt3, Ac2O, and a catalytic amount of palladium complexes such as PdCl2(PPh3)2 at 120-140-degrees-C under 50 atm of CO. No five-membered ring products were observed. A platinum complex PtCl2(PPh3)2 was also effective as a catalyst. The reaction of 5-phenyl-2,4-pentadienyl bromide with M(CO)(PPh3)3 (M = Pd or Pt) under CO gave the corresponding 6-phenyl-3, 5-hexadienoyl complexes in a high yield, which in turn afforded 2-acetoxybiphenyl in 41-51% yield on heating to 160-degrees-C under 50 atm of CO in the presence of NEt3 and Ac2O. Similar 3,5-hexadienoyl complexes are proposed to be intermediates in the catalytic cyclocarbonylation of 2,4-pentadienyl acetates. On the other hand, PdCl2(PPh3)2-catalyzed carbonylation of o-(bromomethyl)(1-alkenyl)-benzenes in the presence of NEt3 and Ac2O gave 2-naphthyl acetates in moderate yields, while the reaction in the absence of Ac2O gave five-membered ring products such as 2-indanones or a tricyclic lactone by incorporation of one or two CO molecules, respectively.

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The PdCl2(PPh3)2-Ru3(CO)12 bimetallic system exhibited higher catalytic activity for the formylation of aryl and alkenyl iodides than PdCl2(PPh3)2 or Ru3(CO)12 alone. Thus, in the formylation of iodobenzene (at 70-degrees-C for 1.5 h under 50:50 atm of CO:H-2), the yield of benzaldehyde by PdCl2(PPh3)2-Ru3(CO)12 catalyst (Pd:Ru = 1:2) was about four times as high as that by PdCl2(PPh3)2 alone. Carbonyl complexes of other metals, such as Mn2(CO)10, Co(CO)8, Cr(CO)6, Fe(CO)5, Mo(CO)6 and W(CO)6 were ineffective as the second component of the catalyst. To clarify the mechanism of the synergistic effects, the reaction of PdI(CO-p-Tol)(PPh3)2 with [HRu3(CO)11]- or [HRu(CO)4]-, ruthenium hydride species known to be generated under the catalytic formylation conditions, was performed. The reaction rapidly proceeded at 40-degrees-C nuclear reductive elimination to form p-tolualdehyde, although the reaction with molecular hydrogen was very slow. These results strongly suggest that the improved catalytic activity of the Pd-Ru system is attributable to the high hydrogenolysis activity of in-situ-generated ruthenium hydride species.

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Alpha-deprotonation of molybdenum or tungsten diazoalkane complexes trans-[MF(NN=CR1CHR2R3)(dpe)2][BF4] (1, M = Mo or W, dpe = Ph2PCH2CH2PPh2) by LDA (lithium diisopropylamide) or NaN(SiMe3)2 provides a general route to alkenyldiazenido complexes trans-[MF(NNCR1=CR2R3)(dpe)2] (2). When 1-diazopropane complexes 1b and 1i were deprotonated, the Z-isomers of alkenyldiazenido complexes were predominantly obtained (Z/E = 6-12). The molecular structure of trans-[WF(NNCH=CMe2)(dpe)2].C6H6 (2f.C6H6) was fully characterized by X-ray analysis: C62H61N2WP4F, space group P1BAR (triclinic); a = 13.398 (8) angstrom, b = 19.051 (13) angstrom, c = 11.950 (8) angstrom, alpha = 98.30 (7)-degrees, beta = 114.54 (5)-degrees, gamma = 81.81 (6)-degrees, Z = 2, R = 0.070, R(w) = 0.082. Relatively long N=N and C=C bond distances (1.29 (3), 1.38 (4) angstrom) and short C-N bond distance (1.26 (3) angstrom) in complex 2f.C6H6 as well as the IR data of complexes 2 indicated considerable contribution of a resonance structure where the terminal carbon of the C=C bond is negatively charged. This has been substantiated by the finding that complexes 2 reacted rapidly with alkyl halides or heterocumulenes such as isocyanates and diphenylketene to give the corresponding C-alkylated or acylated diazoalkane complexes in moderate to high yields, respectively. The deprotonation-alkylation reaction of diazoalkane complexes 1 proceeded regioselectively on the carbon atom cis to the lone pair on the nitrogen of the C=N bond, and the repeated deprotonation-alkylation reactions led to the selective alpha,alpha-dialkylation of the diazoalkane ligand. Acylation with excess aryl isocyanates gave the alpha,alpha-diacylated complexes, whose molecular structure was confirmed by X-ray analysis of trans-[WF{NN=CMeCH(CONHPh)2}(dpe)2][BF4] (7a): formula C69H64O2N4WP4F5B, space group P2(1)2(1)2(1) (orthorhombic); a = 13.764 (4) angstrom, b = 35.917 (7) angstrom, c = 12.986 (4) angstrom, Z = 4, R = 0.064, R(w) = 0.069. Reactions of 2 with aldehydes yielded the Aldol-type condensation products. On the other hand, reactions with I2 or CuCl2 caused the oxidative coupling to give novel mu-bis(diazo)alkane complexes, and their dimeric structure was revealed by the X-ray diffraction study of threo-, trans,trans-[(dpe)2WF(NN=CHCHMeCHMeCH=NN)FW(dpe)2][BF4]2.6(C6H6) (threo-14b.6(C6H6)): formula C146H142N4W2P8F10B2, space group C2/c (monoclinic); a = 32.899 (3) angstrom, b = 13.091 (1) angstrom, c = 32.866 (4) angstrom, beta = 109.782 (7)-degrees, Z = 4, R = 0.077, R(w) = 0.078. Electrochemical study of 2 indicated that the oxidative coupling proceeded by the coupling of a cationic species by the one-electron oxidation of 2.

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Novel ruthenium complexes coordinated with various chiral diphosphines were synthesized by reactions of polynuclear [RUCl2(cycloocta-1,5-diene)]n with the respective diphosphines in the presence of triethylamine. The compositions of the complexes thus obtained were varied according to the solvent used (toluene or ethanol). The structures and dynamic properties of the complexes bearing 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (binap) in solution were elucidated by the H-1 and (P{H})-P-31-H-1 NMR measurements. The X-ray diffraction analysis of trans-RuHCl((R)-binap)2 indicated that the conformation of seven-membered chelate rings and the edge-face manner of phenyl groups were almost the same as those of corresponding rhodium complexes.

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The five-coordinate complex [RuH(binap)2]PF6 (I, binap = (R)- or (S)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl) has been found to have sufficient catalytic activity for asymmetric hydrogenation of itaconic acid and other prochiral carboxylic acids under mild conditions. The catalytic hydrogenation of itaconic acid by I was examined under a variety of conditions, and the addition of triethylamine was found to effect high enantioselectivities (&gt; 90% ee). H-1 and P-31 NMR examinations of reaction mixtures of I and itaconic acid under conditions similar to the hydrogenation suggested the formation of ruthenium species containing one binap chelate.

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The scope and limitation of novel palladium- and platinum-catalyzed cyclocarbonylation reactions of 3-arylallyl and 2,4-pentadienyl acetates are described. The detailed mechanism of these reactions is also discussed.

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Palladium-catalyzed cyclocarbonylation of 3,3-diarylallyl acetates afforded 4-aryl-substituted 1-naphthyl acetates where the cyclization occurred selectively on the more electron-rich ring.

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Palladium-catalysed cyclocarbonylation of penta-2,4-dienyl acetates in the presence of NEt3 and Ac2O selectively gives phenyl acetates in good yields.

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Tungsten alkenyldiazenido complexes reacted with isocyanates, isothiocyanate, and diphenylketene to give regioselectively alpha-acylated diazoalkane complexes after protonation. In the reaction of trans-[WF(NNCMe = CH2)(dpe)2] (dpe = Ph2PCH2CH2PPh2) with excess aryl isocyanates, alpha,alpha-diacylated diazoalkane complexes such as trans-[WF{NN = CMeCH(CONHPh)2}(dpe)2][BF4] were obtained, whose structure was determined by the X-ray analysis.

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The oxidative addition of the coordinated chlorobenzene in [CpFe(C6H5Cl)][PF6] to Pd(PPh3)4 proceeds under THF-reflux conditions to give [CpFe{eta-6-[PdCl(PPh3)2]C6H5}][PF6]. X-ray analysis of this complex revealed that the phenyl ring is sigma-bound to Pd and pi-bound to Fe, and that the palladium center takes the cis-configuration. This complex reacts with CO/MeOH, CO/HNEt2, styrene, and methyl acrylate to give methyl benzoate, N,N-diethylbenzamide, stilbene, and methyl cinnamate, respectively, after photolysis.

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Acetoxybenzofurans, acetoxybenzothiophenes, acetoxyindoles, and acetoxycarbazoles were obtained in high yields by cyclocarbonylation of 3-furyl-, 3-thienyl-, 3-pyrrolyl-, and 3-indolylallyl acetates, respectively, in the presence of Ac2O, NEt3, and a catalytic amount of PdCl2(PPh3)2 at 130-170-degrees-C under 50-70 atm of CO. 3-(3-Furyl)allyl and 3-(3-thienyl)allyl acetates cyclized selectively at the 2-position of the heterocyclic nucleus to give 7-acetoxybenzofuran and 7-acetoxybenzothiophene, respectively. The synthetic utility of the reaction was demonstrated by the synthesis of cannabifuran from isothymol.

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Pt(CO)n(PPh3)4-n (n = 0-2) reacts with Ph2CHCOCl under CO to afford diphenylketene and trans-PtHCl(PPh3)2. For this reaction, the rate law is zero order in the platinum complex, first order in Ph2CHCOCl, and first order in free PPh3. A primary isotope effect (k(H)/k(D) = 4.5) was observed in the reaction of Ph2CDCOCl. A mechanism is proposed which involves the rate-determining enolization of Ph2CHCOCl by PPh3 followed by fast abstraction of HCl by a platinum(0) complex.

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A five-coordinate ruthenium complex with the chiral bisphosphine, (R)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP), [RuH(BINAP)₂]PF₆ (1) was prepared. The complex 1 was found to be a mixture of two isomers in solution. The exposure of 1 to hydrogen gas gave a chiral molecular hydrogen complex, trans-[RuH(η²-H₂)(BINAP)₂]PF₆ (2). [RuD(η²-HD)(BINAP)₂]⁺ ion formed by introducing D₂ gas into a THF-d₈ solution of 1 has a H-D coupling constant J(H,D) = 30 Hz (1:1:1), diagnostic of η²-HD complex.

DOI： 10.1246/cl.1988.2055

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Total pages：359   Responsible for pages：20   Language：Japanese   Book type：Scholarly book

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Responsible for pages：2553-2558   Language：English   Book type：Scholarly book

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Total pages：200   Language：Japanese   Book type：Scholarly book

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Language：Japanese   Publishing type：Article, review, commentary, editorial, etc. (trade magazine, newspaper, online media)   Publisher：化学工業社  

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In this review, we describe the chemistry of seleno- (CSe) and tellurocarbonyl (CTe) complexes, which are heavy congeners of carbonyl (CO) complexes. The survey focuses mainly on recent developments made in this area of chemistry in the past 10 years. CSe and CTe complexes reported before 2000 are also reviewed. Metal thiocarbonyls (CS), which have been known for about 40 years. are not discussed in this account because of the existence of excellent up-to-date reviews of this area. (C) 2011 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.ccr.2011.12.002

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The hydrazido complexes trans-[MX(NNH2)(dppe)(2)](+) (3) and cis,mer-[MX(2)(NNH2)(PMe(2)Ph)(3)] (4) (M = Mo, W; X = halogen; dppe = 1,2-bis(diphenylphosphino)ethane), which are readily derived from dinitrogen complexes trans-[M(N-2)(2)(dppe)(2)] (1) and cis-[M(N-2)(2)(PMe(2)Ph)(4)] (2) by protonation with acid, undergo condensation with aldehydes or ketones (RR'C=O) to give a series of diazoalkane complexes, trans-[MX(NNCRR')(dppe)(2)](+) and cis,mer-[MX(2)(NNCRR')(PMe(2)Ph)(3)]. The diazoalkane ligand in those complexes has a singly-bent structure with the N-N-C bond angle of ca. 120 degrees and the essentially linear N-N-M bond, and may be regarded as a four-electron-donating ligand. Owing to the conjugate structure including the metal center M=N-N=CRR', the diazoalkane complexes exhibit various reactivities including nucleophilic addition, deprotonation, conjugate addition, and reductive dimerization. Condensation of hydrazido complexes 3 and 4 with dialdehydes or their equivalents leads to complexes with nitrogen heterocyclic ligands incorporating the terminal nitrogen atom by way of the cyclization of intermediary diazoalkane complexes. By this method are prepared complexes containing phthalimidine, 1,3-dihydro-2H-pyrrol-2-one, 1,5-dihydro-2N-pyrrol-2-one, and pyrrole moieties. Interestingly, the (l-pyrrolyl)imido complexes with dppe ligands trans-[MX(NNCH = CHCH = CH)(dppe)(2)](+) (26; M=Mo, W) undergo unusual electrophilic substitution reactions at the beta-position of the pyrrole ring. Various types of organonitrogen compounds such as acetone azine, pyrazoles, phthalimidines, pyrroles, and N-aminopyrrole are liberateded from the above complexes in good yields. As a typical reaction, pyrrole and N-aminopyrrole are formed by the LiAlH4 reduction of complexes 26. In this reduction, tetrahydrido complexes [MH(4)(dppe)(2)] (M = Mo, W) are obtained as the metal products, which can be converted back to the starting dinitrogen complexes 1. Thus, a synthetic cycle for the formation of pyrrole and N-aminopyrrole from dinitrogen has been accomplished by using dinitrogen complexes 1.

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Diazoalkane complexes have been attracting wide interest because of their rich coordination chemistry. Diazoalkane ligands, derived from either free diazoalkanes or other precursors such as coordinated dinitrogen, azines, and hydrazones, display numerous coordination modes acting as pi- and/or sigma-bound terminal, bridging, or chelating ligands to form mono- or multimetallic complexes. The reactivities of coordinated diazoalkanes are largely affected by their coordination modes. The variety of reactivities observed for these coordinated diazoalkanes is quite different from those of free diazoalkanes. In this review are described the synthesis, structures, and reactivities of diazoalkane complexes.

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