Structural Tungsten-Imido Chemistry: The Gas-Phase Structure of W(NBut)(2)(NHBut)(2) and the Solid-State Structures of Novel Heterobimetallic W/N/M (M = Rh, Pd, Zn) Species

Reference:

Choujaa, H., Cosham, S. D., Johnson, A. L., Kafka, G. R., Mahon, M. F., Masters, S. L., Molloy, K. C., Rankin, D. W. H., Robertson, H. E. and Wann, D. A., 2009. Structural Tungsten-Imido Chemistry: The Gas-Phase Structure of W(NBut)(2)(NHBut)(2) and the Solid-State Structures of Novel Heterobimetallic W/N/M (M = Rh, Pd, Zn) Species. Inorganic Chemistry, 48 (5), pp. 2289-2299.

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Official URL:

http://dx.doi.org/10.1021/ic8021134

Abstract

The gas-phase (electron diffraction) and solid-state (X-ray) structures of W(NBut)(2)(NHBut)(2) (1) have been determined. In the gas phase, 1 adopts both C-1, and C-2 conformations in a 69:31 ratio. The solid-state structure is disordered over two equal sites, both showing approximate C-2 conformation as in the gas phase; the imido and amido centers are, however, clearly distinguished. Compound 1 has been used to synthesize novel heterobimetallic derivatives. W(NBUt)(4)[Rh(COD)](2) (3) and W(NBut)(4)[Pd(eta(3)-C3H5)](2) (4) via the dilithiated intermediate Li-2[W(NBut)(4)] (2). In both cases, the [W(NBut)(4)] moiety bridges the two organometallic fragments. Reaction of 1 with Me2Zn has produced [Me((BuN)-Bu-t)W(mu-NBut)(2)ZnMe(NH2But)] (5). The structures of 3, 4, and 5 have been determined. Thermal decomposition of 4 under an autogenerated pressure at 700 degrees C has formed the hitherto uncharacterized bimetallic alloy WPd2.

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