Reactivity of the [ReNR]3+ and [ReN]2+ cores toward bis(diphenylphosphino)amine and its derivatives. Synthesis and crystal structures

Abstract

The complexes fac-[Re(NMe)Cl₃{NH(PPh₂)₂-P,P′}]1, [ReNCl{NH(PPh₂)₂-P,P′}₂]X (X = Cl 2 or BPh₄2a), [Re(NMe) Cl₂{N(XPPh₂)₂-X,X′}(PPh₃)](X = 0 3, S 4 or Se 8), [Re(NMe)Cl{N(XPPh₂)₂-X,X′}₂](X = S 5 or Se 9), [ReNCl{N(SPPh₂)₂-S,S′}(PPh₃)]6, [ReN{N(XPPh₂)₂-X,X′)₂](X = S 7 or Se 10) and trans-[ReOCl₂{N(OPPh₂)₂-O,O′}(AsPh₃)]11 were obtained by treatment of [Re(NMe)Cl₃(PPh₃)₂], [ReNCl₂(PPh₃)₂] or [ReOCl₃(AsPh₃)₂] with the appropriate ligand under different experimental conditions. The structures of complexes 1, 2a and 6 were determined by X-ray crystallography. In 1 and 2a the Re atom is six-co-ordinate in a distorted octahedral configuration, whereas in 6 the Re atom is five-co-ordinate square pyramidal with the N atom in the apical position.