Early-late heterobimetallic complexes of the general formula Cp*Ir(�-NtBu)MCp2 (M = Ti, Zr, Hf) have been prepared. These congeneric complexes all contain a metal-metal bond between Ir and the group 4 metal, the physical properties of which have been studied by X-ray diffraction, electrochemical, spectroscopic, and computational methods. Oxidative cleavage of the Ir�M bond has been achieved via treatment with 2 equivalents of [Cp2Fe][OTf], affording Cp*IrNtBu and Cp2M(OTf)2. Aryl azides insert into the Ir�M bonds of Cp*Ir(�-NtBu)MCp2 (M = Zr, Hf) before N2 is lost to afford bridging imido complexes of the formula Cp*Ir(�-NtBu)(�-NAr)MCp2. The kinetics of N2 extrusion from Cp*Ir(�-NtBu)(�-N3Ar)MCp2 have been studied and will be compared. The synthesis of other, new bimetallic compounds will also be discussed.

Early-late heterobimetallics: A comparison of physical properties and reactivity

242nd National Meeting (2011)

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