Abstract
The tetracarbonyl(phosphinothioformimidate) complexes (CO) 4 MSC(NR)P Ph 2 (M = Mn: R = Me, Ph; M = Re: R = Me) were treated with a series of organophosphorus ligands, L, to investigate the substitution of octahedral complexes with unsymmetrical P, S-chelate ligands. Where L = PEt 3, MePPh 2, 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 π 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 = PPh 3 and PCy 3, but the facial forms 5a, 6a with L = ClPPh 2 and HPPh 2. Also, the sterically less crowded rhenium complexes 11a (L = PPh 3) and 12a (L = P(OMe) 3) definitely prefer the facial configuration. A disubstituted manganese complex all- cis-(CO) 2L 2 MnSC(NMe)P Ph 2 ( 8c) was formed only with L = P(OMe) 3. The results show that the influence of phosphorus in P, S-chelate ligands on the stereochemical course of the CO substitution dominates.
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