Reversible Scission of Coordinated Acetylide Ligand: Characterization and Reactivity Studies of WRu4 and WRu5 Carbide-Alkylidyne Clusters

Reversible C−C Bond Cleavage and Interconversion of the Resulting Hydrocarbyl Ligands on Butterfly Frameworks Derived from Acetylide Complexes Cp*WOs3(μ4-CCR)(CO)11(R = Ph,nBu, CH2OMe, CH2OPh)

“…In this article, we address the studies of acetylide C−C bond cleavage through pyrolysis of the species Cp*WOs 3 (CCR)(CO) 11 (R = Ph, n Bu, CH 2 OMe, CH 2 OPh), which leads to an in-depth understanding of the reversible scission of acetylide in small metal clusters induced by CO elimination. This chemistry supplements our previous report on the reversible interconversion of the acetylide cluster CpWRu 2 (CCPh)(CO) 8 and the carbido−alkylidyne clusters CpWRu 4 (μ 5 -C)(μ-CPh)(CO) 12 and CpWRu 5 (μ 6 -C)(μ-CPh)(CO) 14 , promoted by cluster building and degradation reactions . Portions of this work have been reported as a preliminary communication …”

“…This chemistry supplements our previous report on the reversible interconversion of the acetylide cluster CpWRu 2 (CCPh)(CO) 8 and the carbidoalkylidyne clusters CpWRu 4 (µ 5 -C)(µ-CPh)(CO) 12 and CpWRu 5 (µ 6 -C)(µ-CPh)(CO) 14 , promoted by cluster building and degradation reactions. 14 Portions of this work have been reported as a preliminary communication. 15 Experimental Section General Information and Materials.…”

Stepwise Formation of Heterometallic Cluster Compounds (C5Me5)WRu5(μ6-C)(μ-CCH2Ph)(μ-H)2(CO)13and (C5Me5)WRu5(μ4-C)(μ3-CCH2Ph)(μ-H)4(CO)12from Ru5(μ5-C)(CO)15. Reactivity Studies of Carbido Clusters Bearing Acetylide Ligands

“…Thus, treatment of 3 with a CO atmosphere at elevated temperature produced the new octahedral cluster compound (C 5 Me 5 )WRu 5 (μ 6 -C)(μ-CCH 2 Ph)(CO) 14 ( 5 ) in 40% yield, which can react with H 2 to re-form the parent WRu 5 cluster compound 3 in approximately 60% yield. The characterization of 5 was achieved by comparing the spectroscopic data with those of the derivatives LWRu 5 (μ 6 -C)(μ-CPh)(CO) 14 (L = Cp, C 5 Me 5 ), which have been identified by X-ray structural analysis …”

Acetylide derivatives of transition metal cluster carbonyls

“…Treatment of a solution of cluster 31a in hydrocarbon solvents with molecular hydrogen afforded the trihydride complex with the carbvne ligand, vi7..., Ru3(p-H)flCO)9(,u3-CCH2CMe3) (91). :75 It was suggested that m the course of hydrogenation, the dihydride alkyne complex Ru3(p-H)2(CO)9(,u3-q2-HC2Bu t) and the dihydride vinylidene complex Ru3(,u-H)2(CO),~(~t3-q-'-C=C(H)Bu ~) were formed as intermediates.…”