PROMOTION OF ME/CO MIGRATORY INSERTION BY TRANSITION-METAL LEWIS-ACIDS - SYNTHESIS AND REACTIVITY OF A TRANSITION-METAL HETEROBIMETALLIC CARBONYL ALKYL ANION, MEFEW(CO)9-
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The heterobimetallic alkyl anion 1 was prepared by alkylation of FeW(CO)92-using MeI or MeOTs. Addition of the monometallic MeFe(CO)4-to a solution of W(CO)5THF produced the same product. Spectroscopic data indicated the structure of 1 to be analogous to that of HFeW(CO)9-or Ph3AuFeW(CO)9-, i.e., containing octahedral metal centers with a CH3 group bound to Fe, cis to the Fe-W bond. A comparative rate study of the reaction of with monomeric MeFe(CO)4-and with 1 indicated the promotional effect of W(CO)50for the Me/CO migratory insertion reaction. There was no reaction of MeFe(CO)4-with CO2, whereas bimetallic 1 readily added CO2yielding MeC(O)OW(CO)5-. With CS2 a heterobimetallic, formulated as -MeCS2FeW(CO)8-, was produced. 1988, American Chemical Society. All rights reserved.