Octahedral rhodium and iridium {(Ph2P-o-CH2-C6H4)3E}MClH (M = Rh-1, Ir-1: E = Si; M = Rh-2, Ir-2: E = Ge) complexes bearing EP3-type tetradentate ligands were synthesized via E-H bond activation. The new complexes were accessed from the reaction between ligands {(Ph2P-o-CH2-C6H4)3EH with Rh(I), and Ir(I) precursors. Moreover, we describe the synthesis and characterization of platinum {(Ph2P-o-CH2-C6H4)3E}PtH (Pt-1: E = Si; Pt-2: E = Ge) complexes supported by EP3-type tetradentate ligands. The solid-state structures of Rh-1, Rh-2, Ir-1, Ir-2, Pt-1 were confirmed by X-ray crystallography. The catalytic activity of the synthesized rhodium complexes was investigated in the hydrosilylation of alkenes in the presence of triethylsilane (Et3SiH). Excellent conversion, selectivity, and functional group tolerance were achieved.

Synthesis, structure, and reactivity of platinum group metal complexes bearing E-substituted (E = Si, Ge) semirigid phosphine ligands and their application in catalytic alkene functionalization

ACS Fall 2021

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