420
Organometallics 1983,2, 420-425
to singly metal-metal bonded organometallic complexes is the only reaction competitive with metal agglomeration in a polar organic solvent. The observation that in BMTHF at 150 K is reduced by V, Cr, and Fe atoms but not by Ni atoms, while [ ( V ~ - C ~ H ~ ) M O (isCreduced O)~]~ by Ni atoms, but Re2(CO)lois not reduced by V atoms, is consistent with the reduction potentials reported for these metal-metal bonded systems." The solution-phase preparative studies indicate that multimetallic clusters can be synthesized by nucleophilic attack of toluene solvated metal atoms by organometallic anions, either generated in situ by the electron-transfer reaction described above or added directly as the organometallic reagent. The reaction of solvated iron atoms with Mn2(CO)loor M n ( C 0 ) c is, however, complicated by solvent effects and the availability of several competing
reaction pathways of the type indicated in Scheme I. With the experiences gained from this initial study, we have now turned our attention to the reactions of solvated metal atoms with multiple metal-metal and metal-carbon bonds, where the electron-transfer reaction may be minimized and other pathways are expected to predominate.
Acknowledgment. The financial assistance of the National Research Council of Canada's operating grant program is gratefully acknowledged. Registry No. Fe, 7439-89-6;V, 7440-62-2;Cr, 7440-47-3;Ni, 7440-02-0;Mn2(CO),,,, 10170-69-1;[ (&C,H,)MO(CO),]~, 1209113859-41-1;KMn(CO),, 15693-51-3;Re2(CO),o, 64-4; N~[MII(CO)~], 14285-68-8; MO(CO)~,13939-06-5; Fe(toluene)2,69006-35-5; FeMn(CO)9-,84143-94-2;Fe2Mn(CO),
