Binary Carbonyls, Carbonyls plus Hydrides, Carbonyls plus Phosphines, Cyclic Hydrocarbyls and Main-group Ligands without Acyclic Hydrocarbyls

A new synthetic route towards the mixed-metal cluster [Os 2 -Ru(CO) 12 ] is described together with the syntheses of its PPh 3 and iPr-AcPy (iPr-AcPy = 2-acetylpyridine-N-isopropylimine) derivatives. The molecular structures of the novel clusters [Os 2 Ru(CO) 11 (PPh 3 )] and [Os 2 Ru(CO) 10 (iPr-AcPy)] were determined on the basis of crystalline solid solutions of the Os 2 Ru and corresponding Os 3 species. The structures reveal that coordination of the Lewis bases occurs exclusively at the ruthenium site of [Os 2 Ru(CO) 12 ], which is in agreement with density functional theory (DFT) calculations on several structural isomers of these compounds. According to the time-dependent DFT results, the lowest optically accessible excited state of [Os 2 Ru(CO) 10 (iPr-AcPy)] has a prevailing σ(Ru-Os2)-π*(iPr-AcPy) character, with a partial σσ*(Ru-Os2) contribution. In weakly coordinating 2-chlorobutane, the excited state has a lifetime τ = 10.4 ± 1.2 ps and produces biradicals considerably faster than observed for [Os 3 (CO) 10 (iPr-AcPy) (τ = 25.3 ± 0.7 ps). In coordinating acetonitrile, the excited state of [Os 2 Ru(CO) 10 (iPr-AcPy)] decays mono-exponentially with a lifetime τ = 2.1 ± 0.2 ps. In contrast to [Os 3 (CO) 10 (iPr-AcPy)]

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Syntheses and Structures of Mixed-Metal Sulfido Clusters Containing Trimetallic M₂M‘S₄(M = Mo, W; M‘ = Pd, Pt) and Tetrametallic Cubane-Type Mo₂Pd₂S₄Cores

Ikada

Kuwata

Mizobe

et al. 1998

Inorg. Chem.

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The reaction of the sulfido-bridged dimolybdenum or ditungsten complex [M 2 S 2 (µ 2 -S) 2 (S 2 CNEt 2 ) 2 ] (M ) Mo (1a), W) with an equimolar amount of [M′(PPh 3 ) 4 ] (M′ ) Pd, Pt) gave a series of mixed-metal sulfido clusters with a trimetallic M 2 M′ core [M′(PPh 3 )(µ 2 -S) 2 {M(S 2 CNEt 2 )} 2 (µ 2 -S) 2 ]. The X-ray diffraction study for [Pt(PPh 3 )(µ 2 -S) 2 {W(S 2 CNEt 2 )} 2 (µ 2 -S) 2 ] (3b) has disclosed the presence of a novel triangular framework, for which the two Pt-W edges are each bridged by one µ 2 -S ligand and the remaining W-W edge is supported by two µ 2 -S ligands. Cluster 3b crystallized in the monoclinic system, space group C2/c with a ) 13.718(3) Å, b ) 12.795(2) Å, c ) 43.798(2) Å, β ) 95.24(1)°, and Z ) 8. Refinement by full-matrix least-squares techniques gave final residuals R ) 0.052 and R w ) 0.038. Treatment of [Pd(PPh 3 )(µ 2 -S) 2 {Mo(S 2 CNEt 2 )} 2 (µ 2 -S) 2 ] with an additional amount of [Pd(PPh 3 ) 4 ] resulted in the formation of the cubane-type mixed-metal sulfido cluster [{Pd(PPh 3 )} 2 {Mo(S 2 -CNEt 2 )} 2 (µ 3 -S) 4 ], which was also obtained straightforwardly from the reaction of 1a with 2 equiv of [Pd(PPh 3 ) 4 ].

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Binary Carbonyls, Carbonyls plus Hydrides, Carbonyls plus Phosphines, Cyclic Hydrocarbyls and Main-group Ligands without Acyclic Hydrocarbyls

Cited by 5 publications

References 552 publications

The Heteronuclear Cluster Chemistry of the Group 11 Metals – Some Recent Advances

The Heteronuclear Cluster Chemistry of the Group 11 Metals – Some Recent Advances

Heterosite Effects in Novel Heteronuclear Clusters [Os₂Ru(CO)₁₁(PPh₃)] and [Os₂Ru(CO)₁₀(2‐acetylpyridine‐N‐isopropylimine)]

Syntheses and Structures of Mixed-Metal Sulfido Clusters Containing Trimetallic M₂M‘S₄(M = Mo, W; M‘ = Pd, Pt) and Tetrametallic Cubane-Type Mo₂Pd₂S₄Cores

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Binary Carbonyls, Carbonyls plus Hydrides, Carbonyls plus Phosphines, Cyclic Hydrocarbyls and Main-group Ligands without Acyclic Hydrocarbyls

Cited by 5 publications

References 552 publications

The Heteronuclear Cluster Chemistry of the Group 11 Metals – Some Recent Advances

The Heteronuclear Cluster Chemistry of the Group 11 Metals – Some Recent Advances

Heterosite Effects in Novel Heteronuclear Clusters [Os2Ru(CO)11(PPh3)] and [Os2Ru(CO)10(2‐acetylpyridine‐N‐isopropylimine)]

Syntheses and Structures of Mixed-Metal Sulfido Clusters Containing Trimetallic M2M‘S4(M = Mo, W; M‘ = Pd, Pt) and Tetrametallic Cubane-Type Mo2Pd2S4Cores

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Heterosite Effects in Novel Heteronuclear Clusters [Os₂Ru(CO)₁₁(PPh₃)] and [Os₂Ru(CO)₁₀(2‐acetylpyridine‐N‐isopropylimine)]

Syntheses and Structures of Mixed-Metal Sulfido Clusters Containing Trimetallic M₂M‘S₄(M = Mo, W; M‘ = Pd, Pt) and Tetrametallic Cubane-Type Mo₂Pd₂S₄Cores