Reactivity of Cp‘2Mo2Co2S3(CO)4with Diphosphines: Synthesis of Cp‘2Mo2Co2S3(μ3-CO)(η2-dmpe)2and X-ray Structure of [Cp‘2Mo2Co2S3(μ3-CH)(η2-dmpe)2]Cl
Owen J. CurnowM. David CurtisJeff W. Kampf
Abstract
Treatment of the heterobimetallic sulfido cluster Cp'2Mo2Co2S3(CO)4 (1) with the diphosphine compound bis(diphenylphosphino)methane (dppm) or bis(diphenylphosphino)ethane (dppe) gives the carbonyl-substituted adduct Cp'2Mo2Co2S3(CO)2(η2-dppm) (11a) or Cp'2Mo2Co2S3(CO)2(η2-dppe) (11b), respectively, whereas treatment of 1 with an excess of bis(dimethylphosphino)ethane (dmpe) gives the cluster Cp'2Mo2Co2S3(μ3-CO)(η2-dmpe)2 (12) containing a triply-bridging carbonyl ligand (νCO = 1615 cm-1). Cluster 12 readily reacts with dichloromethane to give the μ3-methylidyne cluster [Cp'2Mo2Co2S3(μ3-CH)(η2-dmpe)2]+ (14). Cluster 14 was also characterized by an X-ray crystallographic analysis. Reaction of 13CO-labeled 12 with CH2Cl2 and CD2Cl2 showed that the methylidyne atoms originate from the dichloromethane solvent. 13CO-labeled 1 was prepared to 96% enrichment and revealed a resonance for the carbonyl ligands in the 13C-NMR spectrum at δ 207 with w1/2 = 940 Hz. Cluster 11b was found to desulfurize thiols and perform phosphinidene abstraction reactions via formation of the monomeric cluster Cp'2Mo2Co2S4(η2,μ2-dppe) (18) or the oligomeric clusters [Cp'2Mo2Co2S3(μ3-PPh)(η2,μ2-dppe)]n (19), respectively.
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