Carbonyl complexes of molybdenum and tungsten with sulfur donors VI. Reactions of carbonyl complexes of molybdenum(0) and tungsten(0) with uninegative (S,X)-donor ligands (X = S, N, P)

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The reactions of the zerovalent carbonyl complexes, M(CO) 6, M(CO) 5(Rpy), M(CO) 4(Rpy) 2 (M = Mo, W, R = 2-Me, H) with a series of potentially mono- or bi-dentate uninegative (S,X)-donor ligands (S,X = xanthates, dithiocarbamates, pyridine-2-thiol, P,P-diphenyl- N-phenylphosphinothioformomido, P,P-diphenylphosphinedithioformamide) have given two types of anionic complexes: [M(S,X)(CO) 5] − and [M(S,X)(CO) 4] − (M = Mo 0, W 0). These anions, which contain the (S,X)-ligand as a mono- or bi-dentate group, respectively, were isolated as their tetraphenylphosphonium or triethylammonium salts. Reactions of some of these species with allyl bromide and HgX 2 are described. The crystal structure of [PPh 4][W(S 2COEt)(CO) 5] has been determined. The crystals are monoclinic, space group P2 1/ n with a 14.555(4), b 12.44(1), c 17.950(2) Å, U 3145.9(3) Å 3, Z = 4; D c 1.65 g cm −3, μ(Mo- K α) 39.68 cm −1, F(000)_= 1544, R = 0.042 for 4278 observed reflections. In this complex the xanthate ligand is monodentate.