Regioselective ortho‐Metallation of 2‐Diphenylphosphanylpyridine and (2‐(2‐Diphenylphosphanyl)phenyl)‐1‐3‐dioxalane with Methyltetrakis(trimethylphosphane)cobalt(I)

Abstract

AbstractCo(CH3)(PMe3)4 forms 100 % regioselectively with (2‐(2‐diphenylphosphanyl)phenyl)‐1,3‐dioxalane and 2‐diphenylphosphanyl‐pyridine, by elimination of methane, the four‐membered metallacycles Co{(C3O2HC6H3)P(C6H5)2}(PMe3)3 (1) and Co{(CNC4H3)P(C6H5)2}(PMe3)3 (4). The regioselectivity is independent of the steric requirement of the ortho substituent in the 2‐diphenylphosphanylaryl‐ligands. Oxidative addition with iodomethane transforms 1 and 4 into octahedral, diamagnetic low‐spin d6 complexes Co(CH3)I‐{(C3O2HC6H3)P(C6H5)2}(PMe3)2 (2) and Co(CH3)I‐{(CNC4H3)P(C6H5)2}(PMe3)2 (5). Under an atmosphere of carbon monoxide, insertion into the Co‐C bond results in ring expansion by forming the new assembled phosphanylbenzoyl complexes Co{(C4O3HC6H3)‐P(C6H5)2}CO(PMe3)2 (3) and Co{(OCNC4H3)P(C6H5)2}CO(PMe3)2 (6). The three different types of cobaltacycles are supported by X‐ray diffraction of 1, 3, 5 and 6.