Organosilicon chemistry. Part 23. Some silylcobalt(III) complexes and the homogeneous catalysis of deuteriation, hydrosilylation, and O-silylation reactions

Abstract

The complexes [CoH(X₂)L₃](X = H or N; L = PPh₃) react with silanes, SiR₃H, to give the new silylcobalt(III) complexes [CoH₂(SiR₃)L₃][R₃= F₃, MeF₂, or (OEt)₃]. The characterization of these complexes and their reactions with N₂, H₂, HCl, CCl₄, and CO are described. With CO the new cobalt(I) silyl [Co(SiF₃)(CO)₂L₂] is formed. The stability of the silyls to loss of SiR₃H decreases as the electronegativity of R decreases, which allows the less-stable complexes to participate in catalytic processes. The reaction of SiR₃H with D₂(R = F, OEt, Et, or Me), of SiH(OEt)₃ or Me₃Si[OSi(H)Me]_nOSiMe₃ with EtOH, and of SiH(OEt)₃ with hex-1-ene are catalysed by [CoH(X₂)L₃] or by [CoH₂{Si(OEt)₃}L₃]. The deuteriation reaction provide an easy routr to deuteriosilanes, SiR₃D.