Abstract
Comolexes cis-[Ru(CO)2L2X2](L = ligand with phosphorus or arsenic donor atom. X = haloaen) are converted to their all-trans-isomers by u.v. radiation; the process can be reversed by heating. Similar rearrangements occur with complexes [Ru(CO)2LL′Cl2] containing Two different phosphorus ligands L and L′. Studies of the thermal rearrangements of complexes all-trans-[Ru(CO)2(PMe2Ph)2X2] and all-trans-[Ru(CO)2(PMePh2)2X2] show that they occur by two competing routes, one direct and one by way of a third isomer, the all-cis-isomer. Evidence from these studies and from the stereochemistry of carbonyl-substitution reactions of the various isomers of [Ru(CO)2(PMe2Ph)2Cl2] is presented to support mechanisms for the photochemical and thermal isomerizations which involve dissociation of a carbonvl liaand as a first step During the isomerizations, partial loss of CO from solution causes the formation of complexes [{Ru(CO)L2X2}2] as by-products.
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