LIGAND SUBSTITUTION PROCESSES IN TETRANUCLEAR CARBONYL CLUSTERS .8. REACTIONS OF CO4[(CO)-C-12]12/CO4[(CO)-C13]12 WITH PHOSPHORUS DONOR LIGAND SUBSTITUTION PROCESSES
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A possibile mode of reaction for ligand substitution processes involving polynuclear metal carbonyl derivatives is cluster fragmentation followed by recombination. Definitive experiments designed to probe this phenomenon in dinuclear metal carbonyls of the group 7B metals have recently been published. These include studies of thermal ligand substitution reactions involving MnRe(CO)10 or a mixture of Mn2(CO)10/Re2-(CO)10,1185Re2(CO)10/187Re2(CO)10,2 and Mn2(13CO)10/Mn2(12CO)10.3 In these dimeric species, thermal ligand substitution reactions were demonstrated to proceed via carbon monoxide dissociation from the intact dimer (Scheme I), as opposed to Scheme II, which entails metal-metal bond homolysis. 1984, American Chemical Society. All rights reserved.