Syntheses of Iminophosphomamido Chlorogermylenes and Their Complexation with a Rhodium(I) Complex

Abstract

AbstractThree‐coordinated chlorogermylenes of the type [Ph2P(RN)2]GeCl (3: R=tBu; 4: R=Dip=2,6‐iPr2C6H3), which bear an N,N‐substituted iminophosphonamide ligand, were synthesized. The coordination behavior of 3 and 4 toward rhodium(I) complex was investigated. When 3 was treated with 1/2 of an equivalent of [RhCl(cod)]2 (cod=1,5‐cyclooctadiene), the corresponding chlorogermylene‐Rh(I) complex 5 was obtained as orange crystals. In contrast, the reaction of 4 with a half equivalent of [RhCl(cod)]2 under a CO atmosphere resulted in the formation of a five‐membered germarhodacycle 7. Compounds 3, 4, 5, and 7 were characterized using NMR spectroscopies and single‐crystal X‐ray diffraction. Complex 5 can be employed as a catalyst for the hydrosilylation and hydroboration reactions of diphenylacetylene, thus demonstrating the utility of germylene ligands comparable to those of NHCs in the major transition metal catalytic processes.