Distinct modes of Si–H binding to Rh in complexes of a phosphine-diarylamido-silane (SiNP) pincer ligand

Abstract

Syntheses of Rh complexes of the phosphine-amido-silane SiNP ligand are reported. The reaction of the parent (SiNP)H ligand (4) with 0.5 equiv. [(COE)RhCl]₂ (COE = cis-cyclooctene) in the presence of NaN(SiME₃)₂ resulted in the formation of (SiNP)Rh(COE) (5). Compound 5 was converted to a series of (SiNP)Rh(P(OR)₃) complexes 6–10 (R = Ph, ⁱPr, ⁿBu, Et, or Me) by treatment with the corresponding phosphite. NMR and XRD structural data, as well as the DFT computational analysis indicate that compounds 5–10 are divided into two structural Types (A and B), differing in the nature of the interaction of the Si–H bond of the SiNP ligand with Rh.