PHOSPHINSUBSTITUIERTE CHELATLIGANDEN. XVI. SUBSTITUTION VON TETRACARBONYL(PHOSPHINOTHIOFORMIMIDAT)-KOMPLEXEN DES MANGANS UND RHENIUMS MIT ORGANOPHOSPHOR-LIGANDEN

Article abstract of DOI:10.1016/0022-328X(85)80221-7

The tetracarbonyl(phosphinothioformimidate) complexes <*> (M=Mn: R=Me, Ph; M=Re: R=Me) were treated with a series of organophosphorous ligands, L, to investigate the substitution of octahedral complexes with unsymmetrical P,S-chelate ligands.Where L=PEt3, MePPh2, P(OMe)3 and P(OPh)3, the facial tricarbonyl complexes 3a,4a,7a,8a,10a and 12a are obtained as kinetic products which rearrange upon warming into the thermodynamically more stable mer form (b).The isomerisation is governed more by steric factors than by the ? acceptor strength of the ligands L and can be correlated with the Tolman parameter θ.The meridional manganese complexes 1b and 2b are obtained with the bulky ligands, L=PPh3 and PCy3, but the facial forms 5a,6a with L=ClPPh2 and HPPh2.Also, the sterically less crowded rhenium complexes 11a (L=PPh3) and 12a (L=P(OMe)3) definitely prefer the facial configuration.A distributed manganese complex all-cis-<*> (8c) was formed only with L=P)OMe)3.The results show that the influence of phosphorous in P,S-chelate ligands on the stereochemical course of the CO substitution dominates.