REACTIONS OF HCCO3(CO)9 WITH SILANES - SYNTHESIS AND ELECTROCHEMISTRYOF X[SIME2CCO3(CO)9]2 (X=O, 1,4-C6H4)

Reactions between Ph(n)SiH4-n or HR2SiXSiR2H and HCCo3(CO)9 are descri bed. Both the monocluster, HMe2SiXSiMe2(CCo3(CO)9, and the discluster, (CO)9Co3CMe2SiXSiMe2CCo3(CO)9, complexes were obtained from the silan es HMe2SiXSiMe2H (X = O, 1,4-C6H4). RSiH2CCo3(CO)9 (R = Ph, Me) or ste rically demanding silanes do not couple with HCCo3(CO)9. Generally wit h Ph(n)SiH4-n (n = 1, 2) electrophilic attack on the cluster core resu lted in the formation of the novel mu-silylene complexes HCCo3(CO)8(mu -SiR2), and fragmentation of the Co3C unit, instead of the expected si licon-bridged diclusters. Electrochemical investigation of the diclust er compounds and their phosphite derivatives showed there was no inter action between the cluster redox centres.