Molybdenum and tungsten complexes with the heteroallyl-like Ph 2P(O)C(S)NR − (R  Me, Ph) as ligand. X-ray structural analysis of Mo(CO) 2(PPh 3)(Ph 2P(O)C(S)NPh) 2 · CH 2Cl 2; A 4 : 3 piano-stool configuration

Abstract

Ph 2P(O)C(S)N(H)R (R  Me, Ph) reacts with M(CO) 3(η 5-C 5H 5)Cl (M  Mo, W) in the presence of Et 3N to give M(CO) 2(η 5-C 5H 5)(Ph 2P(O)C(S)NR). The deprotonated ligand coordinates in a bidentate manner through N and S to give a four-membered ring system. M(CO) 3(PPh 3) 2Cl 2 (M  Mo, W) reacts with Ph 2P(O)C(S)N(H)R (R  Me, Ph) in the presence of Et 3N to give complexes in which the central metal atoms are seven coordinate through two ligands bonded via O and S to form five-membered ring systems, one PPh 3, and two CO groups. The complexes were characterised by elemental analyses, IR, 1H NMR, and 31P NMR spectroscopy, and an X-ray structural analysis of Mo(CO) 2(PPh 3)(Ph 2P(O)C(S)NPh) 2 · CH 2Cl 2.