REACTIVITY OF THE [RENR]3+ AND [REN]2+ CORES TOWARD BIS(DIPHENYLPHOSPHINO)AMINE AND ITS DERIVATIVES - SYNTHESIS AND CRYSTAL-STRUCTURES

The complexes fac-[Re(NMe)Cl3{NH(PPh2)2-P,P'}] 1, [ReNCl{NH(PPh2)2-P,P'}2]X (X = Cl 2 or BPh4 2a), [Re(NMe)Cl2{N(XPPh2)2-X,X'}(PPh3)] (X = O 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.