Treatment of the germyl complex [Rh(GePh 3 )(PEt 3 ) 3 ] (1) with CS 2 afforded the rhodium thiocarbonyl complex trans-[Rh(SGePh 3 )(CS)(PEt 3 ) 2 ] (2) by phosphine dissociation and C-S bond activation. The analogous reaction with COS gave the structurally related carbonyl complex trans-[Rh(SGePh 3 )(CO)-(PEt 3 ) 2 ] (3). Low-temperature NMR measurements revealed initial formation of the intermediates mer-[Rh(GePh 3 )(η 2 -CS 2 )-(PEt 3 ) 3 ] (4) and mer-[Rh(GePh 3 )(η 2 -COS)(PEt 3 ) 3 ] (5). Reactions of 2 towards CO and HCl led to the replacement of the thiocarbonyl or germylthiolato ligand yielding complex 3 and trans-[a] 715 Scheme 2. Possible mechanism for the formation of complexes 2 and 3.
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