| Abstract: | Co(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 . |
