Abstract
Complexes of rhodium(I) with carbon monoxide, bis(diphenylphosphino)methane (dppm), or the arsine analogue (dpam), and a variety of anionic ligands are described, and the natures of each of the novel complexes are compared with those of known complexes containing terminal or bridging chloro-ligands. In solution in acetone–methanol and in the presence of halide ions (X = Cl, Br, or I) cationic dinuclear ‘A-frame’ complexes [Rh2(µ-X)(CO)2L2]+ and [Rh2(µ-X)(µ-CO)(CO)2L2]+(L = dppm or dpam) are readily formed. In the presence of the pseudohalide ions (Z = CN or SCN) the neutral complexes [Rh2Z2(CO)4L2] are initially formed. The cyano-complexes readily dissociate one (dppm) or two (dpam) moles of CO respectively. When Z is OCN or N3 the products are dinuclear dicarbonyl complexes [Rh2Z2(CO)2L2].

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