Affiliation:
1. Department of Chemistry University of Oxford Chemistry Research Laboratory 12 Mansfield Road Oxford OX1 3TA United Kingdom
2. Department of Chemistry Indiana University 800 E. Kirkwood Ave. Bloomington IN 47405 U.S.A
Abstract
AbstractReaction of a nucleophilic germylene Ge[CH(SiMe3)2]2 with the phosphanyl phosphaketene [{(H2C)(NDipp)}2P]PCO induces decarbonylation to form a phosphanyl phosphagermene [{(H2C)(NDipp)}2P]P=Ge[CH(SiMe3)2]2 (1; Dipp=2,6‐diisopropyl‐phenyl). Addition of CO2 or MeCN to 1 results in [3+2]‐cycloaddition reactions to afford five‐membered heterocycles. This mode of reactivity is reminiscent of that observed for frustrated Lewis pairs, with the pendant phosphanyl group acting as a base and the germanium center as a Lewis acid. Contrastingly, 1,2‐addition across the P=Ge bond was observed when using ammonia, small primary amines (NH2nP), or metal complexes (e. g. Au(PPh3)Cl and ZnEt2). These latter reactions allow for the one‐step synthesis of metal phosphide complexes.
Funder
Engineering and Physical Sciences Research Council