Coordination chemistry of stibine and bismuthine ligands

The Coordination and Bioinorganic Chemistry of Molybdenum

Publisher Summary Recently, an article was published on 1,2-dithio ligands, and have stressed the versatility of these ligands and the academic and industrial importance of their metal complexes. Complexes of molybdenum and tungsten with bidentate sulfur ligands have been investigated extensively. In recent years, the work in this field has been escalated by the impetus of designing models of such bioinorganic enzymes as nitrogenase and xanthine oxidase. Oxidation of copper dithiocarbamate complexes of Cu(1) with chlorine or bromine yields paramagnetic compounds with the composition CuX 3 (R 2 dtc), in which the copper has a formal oxidation-state of (IV), but the structure of these compounds is obscure. The complexes of the 1,1-dithio ligands with the Group I transition metals have been studied in considerable detail and have been extensively reviewed by Coucouvanis.

1, 1-Dithiolato Complexes of the Transition Elements

The chemistry of the dithioacid and 1,1‐dithiolate complexes, 1968‐1977

Electrochemical studies of oxo- and sulfido-bridged molybdenum(VI), -(V), and -(IV) diethyldithiocarbamate complexes in aprotic solvents

Complexes of the type Mo(CO)2RPh3(dtc)2 (R = P, As, Sb; dtc = dialkyldithiocarbamato) have been prepared by the interaction of sodium dialkyldithiocarbamates with, for example, dichlorobis(triphenylphosphine)trioarbonylmolybdenum(11). In solution the complexes are susceptible to oxidation, but the product obtained depends strongly upon the nature of the solvent used. In acetone solution oxidation yields complexes of the type No2O3(dtc)4; this reaction is very similar to that reported previously for the oxidation of the parent compounds Mo(CO)3(dtc)2 and Mo(CO)2(dtc)2. However, oxidation of Mo(CO)2RPh3(dtc)2 in carbon tetrachloride-benzene mixture gives molybdenum(VI) derivatives of empirical formulae MoO2(dtc)2. The properties of these compounds are different from those reported by Moore and Larson for other compounds of the same formula. Infrared and mass spectrometric studies have shown that our complexes are dimeric and it has been confirmed that those of Moore and Larson are monomeric.

GG Rose

Papers

Carbonyl halides of the Group VI transition metals. XX. Substituted dialkyldithiocarbamato complexes of molybdenum halocarbonyls and their oxidation