A facile route to carbonylhalogenometal complexes (M = Rh, Ir, Ru, Pt) by dimethylformamide decarbonylation

Dimethyl formamide (DMF) can be a convenient source of the carbonyl ligand in the coordination chemistry of rhodium, ruthenium, iridium, and platinum. We have undertaken a thorough study concerning the course of this reaction . In a first step, DMF-containing complexes are produced, which is usually accompanied by chloride redistribution. Then, upon refluxing, carbonyl spec ies in the same oxidation state are obtained, presumably as a result of HCl -mediated DMF decomposition. Provided that water levels are kept low, reduc tion can occur to provide the complexes [NH2(CH3)(2)][RhCl2(CO)(2)], [NH2(C H3)(2)][RuCl3(CO)(2)(DMF)], [RuCl2(CO)(2)(DMF)(2)], and [NH2(CH3)(2)][IrCl2 (CO)(2)]. In the case of platinum, reduction is not effective and [NH2(CH3) (2)][PtCl3(CO)] is obtained. No carbonylpalladium species can be synthesize d in this way, the reaction producing copious amounts of colloidal metal. A dding phosphanes to these chlorocarbonyl-containing solutions allows easy, one-step syntheses of a variety of complexes.