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

Dalton Trans. 2022 Sep 26;51(37):14150-14155. doi: 10.1039/d2dt02175g.

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.