“Grignard‐Analogous” Rhodium Phosphane Complexes

Abstract

Interesting stoichiometric and catalytic reactions are possible with the rhodium phosphane complexes [{Ph2P(CH2)nPPh2}2Rh][MgCl] (1: a, n = 2; b, n = 3), which are readily accessible by reaction of the chloride complexes 2 with active magnesium. The “Grignard-analogous” compounds 1 react to form 3 (E = H, Me, SiMe3) by protolysis, alkylation, and silylation. The interconversion of complexes 2a and 1a can be used for catalytic transfer of two electrons from magnesium to CO2 to yield CO and CO.