Manganese and rhenium triphosphorus macrocycle complexes and reactions with alkenes

Abstract

The synthesis of Re(III), Re(I) and Mn(I) compounds of the macrocyclic phosphine ligand 1,5,9-trialkyl-1,5,9-triphosphacyclododecane, 12[ane]P3R3 (R = Et, iBu) is described. The reaction of 12[ane]P3R3 with ReCl3(PPh3)2(CH3CN) or ReCl3(PPhMe2)3 gives rise to the octahedral d4 complexes (12[ane]P3R3)ReCl3 (1R). Reduction of 1iBu with Na/Hg under a CO atmosphere gives the rhenium(I) compound (12[ane]P3R3)Re(CO)2Cl, 2R which undergoes further reactivity to give hydride (3R), vinylidene (4R) and allenylidene (5R) compounds. With Mn(CO)5Br, 12[ane]P3Et3 gives the octahedral d6 complex, (12[ane]P3Et3)Mn(CO)2Br, 6Et. The crystal structures of (12[ane]P3iBu3)ReCl3 and (12[ane]P3Et3)Mn(CO)2Br are presented.