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

• Published in: Inorganic chemistry 2009-03, Vol.48 (5), p.2289-2299
• Main Authors: Choujaa, Hamid, Cosham, Samuel D, Johnson, Andrew L, Kafka, Graeme R, Mahon, Mary F, Masters, Sarah L, Molloy, Kieran C, Rankin, David W. H, Robertson, Heather E, Wann, Derek A
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic8021134

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(η3-C3H5)]2 (4) via the dilithiated intermediate Li2[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(tBuN)W(μ-NBut)2ZnMe(NH2But)] (5). The structures of 3, 4, and 5 have been determined. Thermal decomposition of 4 under an autogenerated pressure at 700 °C has formed the hitherto uncharacterized bimetallic alloy WPd2.