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.