The synthesis and characterisation of several metal complexes of a redox-active, mesityl(Mes)-substituted [1]phosphaferrocenophane, FcPMes (1), are reported. Cyclic voltammetry studies on the bimetallic complexes [M(κ P-1)(cod)Cl] (M=Rh: 2; M=Ir: 4), [Rh(κ P-1) (CO)Cl] (3) and [AuCl(κ P-1)] (5), in conjunction with DFT calculations, provided indications for a good electronic communication between the metal atoms. To confirm that the ferrocenophane unit might be able to electrochemically influence the reactivity of the coordinated transition metal, the rhodium complex 2 was employed as stimuli-responsive catalyst in the hydrosilylation of terminal alkynes. All reactions were greatly accelerated with in situ generated 2 as a catalyst as compared to 2. Even more importantly, a markedly different selectivity was observed. Both factors were attributed to different mechanisms operating for 2 and 2 (alternative Chalk-Harrod and Chalk-Harrod mechanism, respectively). DFT calculations revealed relatively large differences for the activation barriers for 2 and 2 in the reductive elimination step of the classical Chalk-Harrod mechanism. Thus, the key to the understanding is a cooperative "oxidatively induced reductive elimination" step, which facilitates both a higher activity and a markedly different selectivity.
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