Synthesis and structures of technetium(I) and rhenium(I) tricarbonyl complexes with bis(dilphenylthiophosphoryl)amide, {M(CO)3[(Ph2PS)2N](CH3CN)} (M = Tc, Re)

Article abstract of DOI:10.1016/S0277-5387(97)00344-6

Complexes of the general formula {M(CO)₃[(Ph₂PS)₂N](CH₃CN)} (M = Tc, Re) have been prepared by the reaction of (Et₄N)₂[M(CO)₃X₃] (M = Tc, Re ; X = Cl, Br) with sodium bis(diphenylthiophosphoryl)amide, Na[(Ph₂PS)₂N], in acetonitrile. The metal is six-coordinate with facially arranged carbonyl ligands. Bis(diphenylthiophosphoryl)amide is deprotonated and bonded as S,S′-chelate with Tc - S distances of 2.526(3) and 2.546(3) A. Acetonitrile occupies the sixth coordination position. The rhenium compound is isomorphous and the bonding situation in {Re(CO)₃[(Ph₂PS)₂N](CH₃CN)} is similar to that in its technetium analogue. (Et₄N)[Re(CO)₃Br₂(CH₃CN)] crystallizes from a hot acetonitrile solution of (Et₄N)₂[Re(CO)₃Br₃] despite the fact that in solution only [Re(CO)₃(CH₃CN)₃]⁺ can be detected spectroscopically. It has a facial arrangement of CO groups in an octahedral co-ordination geometry.