Laser-ion beam photodissociation studies of ionic cluster fragments of transition-metal carbonyls

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 = 0–10, derived from Mn2(CO)10), Fex(CO)y+(x = 3;y = 5–12, derived from Fe3(CO)12), and Cox(CO)y+(x = 2-4; y = 0–12, 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.

Laser-ion beam photodissociation studies of ionic cluster fragments of transition-metal carbonyls Academic Article