LASER ION-BEAM PHOTODISSOCIATION STUDIES OF IONIC CLUSTER FRAGMENTS OF TRANSITION-METAL CARBONYLS
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Ionic cluster fragments of the type Mx(CO)y+are studied by laser-ion beam photodissociation. The systems studied include Mnx(CO)y+ (x = 1-2;y = 010, derived from Mn2(CO)10), Fex(CO)y+(x = 3;y = 512, derived from Fe3(CO)12), and Cox(CO)y+(x = 2-4; y = 012, derived from Co4(CO)12. Relative photodissociation cross sections for each ion and upper limits to bond dissociation energies for M-M and M-CO are reported. Average metal-metal bond energies for the Mn2(CO)y+ and Co4(CO)y+ ions are found to be <44 and 16 kcal/mol, respectively. M-M bond energies could not be determined for Fe3(CO)y+ ions because photodissociation of this system is dominated by expulsion of the CO ligand. Upper limits for metal-ligand bond energies determined are <25, 24, and 23 kcal/mol for Mn2(CO)y+, Fe3(CO)y+, and Co4(CO)y+ systems, respectively. 1987, American Chemical Society. All rights reserved.