Dissociative chemistry of ionic transition metal cluster fragments
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abstract
The ionic fragments formed by collision-induced dissociation of Mn2(CO)y+ ions (y=1-10) are reported. The ratio of product ions formed by metal-metal vs. metal-ligand bond cleavage are discussed in terms of the dependence of the metal-metal bond energy on the metal-to-ligand ratio. The collision-induced dissociation data indicate that the metal-metal bond energy of Mn2(CO)5+ and Mn2(CO)10+ is less than that for Mn2(CO)y+ (y=1-4 and 6-9). The product ions arising by metal-metal and metal-ligand bond cleavage reactions for collision-induced dissociation and photodissociation are compared. On the basis of this data and the known photochemistry/photophysics of Mn2(CO)10, it is proposed that the difference in collision-induced dissociation and photodissociation product ion branching ratios is attributable to spin-orbit transitions of the activated ions. 1991 Plenum Publishing corporation.
