Abstract

The coordination of a novel type of tripodal amido ligand provides the key to the synthesis of stable M-M� (M = Ti, Zr, Hf; M� = Fe, Ru) heterobimetallic complexes, MeSi{SiMe2N(C6H4Me-4)} 3M-M�(η5-C5H5)(CO) 2 4-9, with unsupported metal-metal bonds and thus enables systematic studies of these complexes; the crystal structures of the Ti-Fe (4) and Zr-Fe (6) complexes are reported, the latter being the first X-ray structure of a compound containing a Zr-Fe bond; reaction of the M-M� complexes with methyl isocyanide leads to the immediate insertion into the metal-metal bond, a reaction which is analogous to α-additions to isocyanides.