80977-47-5Relevant articles and documents
Phosphine Substituted Chelate Ligands, III. η5-Cyclopentadienyliron Carbonyl Complexes with Thiocarbamoyl-Phosphine, -Phosphine Sulfide and -Phosphine Oxide Ligands
Kunze, Udo,Antoniadis, Antonios
, p. 1588 - 1594 (2007/10/02)
The reactions of N-silylated and free diphenylphosphino thioformamides, Ph2PC(S)NRR' (R = Ph, Me, Et; R' = Me3Si, H), with CpFe(CO)2I yield, by displacement of one equivalent CO, both red-brown P,S-coordinated chelate complexes 1a-c and green P-coordinated iodo complexes 2a-c.With thiocarbamoylphosphine sulfides, Ph2P(S)C(S)NHR (R = Ph, Me), the S,S'-coordinated chelate complexes 3a,b are obtained.The corresponding phosphine oxides only form deeply coloured, weak 1/1 adducts 4a,b with CpFe(CO)2I.The course of the nucleophilic substitution of CpFe(CO)2X (X = Cl, Br, I) by N-silyl phosphino thioformamides reveals a significant dependence on the halogen employed.For X = Cl, elimination of RNCS and formation of the cationic diiron complex 2PPh2(1+)*Cl(1-) (5a) takes place, whereas for X = Br no reaction occurs at room temperature.Mechanistic reasons for this unexpected behaviour are discussed. - Keywords: Chelate Ligands, Cyclopentadienyliron Complexes, Thiocarbamoylphosphine, Thiocarbamoylphosphine Sulfide, Thiocarbamoylphosphine Oxide
