ALKYLATION OF ORGANOIRON THIOLATE COMPLEXES

Article abstract of DOI:10.1016/S0022-328X(00)99259-3

The iron thiolate complexes Fe(SPh)(CO)(L)(η-C5H5) (L = PMe3, PPh2Me, PPh3, PPh2OMe, PPh(OMe)2, P(OMe)3, P(OPh)3) react with EtBr in CHCl3 (21 deg C) to produce the cationic sulfide complexes, Br.A study of the kinetics of these reactions shows that these reactions are first order in complex and in EtBr; however the rates are largely insensitive to the nature of L in the precursor.After prolonged periods of time, or upon heating, a further reaction ensues in which bromide ion displaces the sulfide ligand to yield FeBr(CO)(L)(η-C5H5).Reactions between Fe(SPh)(CO)2(η-C5H5) and EtBr, and between Fe(SPh)(CO)(PMe3)(η-C5Me5) and EtBr, give FeBr(CO)2(η-C5H5) and FeBr(CO)(PMe3)(η-C5Me5) directly.These reactions presumably also occur via facile ligand loss from the intermediate sulfide complexes.