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

Complexes of the general formula {M(CO)(3)[(Ph2PS)(2)N] (CH3CN)} (M = Tc, Re) have been prepared by the reaction of (Et4N)(2)[M(CO)(3)X-3] (M = Tc, Re; X -Cl, Br) with sodium bis(diphenylthiophosphoryl)amide, Na[(Ph2PS)(2)N], 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) Angstrom. Acetonitrile occupies the sixth coordination position. The rhenium compound is isomorphous and the bonding situation in {Re(CO)(3)[(Ph2PS)(2)N](CH3CN)} is similar to that in its technetium analogue. (Et4N)[Re(CO)(3)Br-2(CH3CN)] crystallizes from a hot acetonitrile solution of (Et4N)(2)[Re(CO)(3)Br-3] 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. (C) 1998 Elsevier Science Ltd. All rights reserved.