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

Hamid Choujaa, Samuel D. Cosham, Andrew L. Johnson, Graeme R. Kafka, Mary F. Mahon, Sarah L. Masters, Kieran C. Molloy, David W. H. Rankin, Heather E. Robertson, Derek A. Wann

Research output: Contribution to journalArticlepeer-review

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 C1 and C2 conformations in a 69:31 ratio. The solid-state structure is disordered over two equal sites, both showing approximate C2 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(ButN))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.

Original languageEnglish
Pages (from-to)2289-2299
Number of pages11
JournalInorganic Chemistry
Volume48
Issue number5
DOIs
Publication statusPublished - 2 Mar 2009

Keywords

  • CHEMICAL-VAPOR-DEPOSITION
  • ATOMIC LAYER DEPOSITION
  • RAY CRYSTAL-STRUCTURES
  • ELECTRON-DIFFRACTION
  • MOLECULAR-STRUCTURE
  • THIN-FILMS
  • ELEVATED-TEMPERATURE
  • AUTOGENIC PRESSURE
  • TRANSITION-METALS
  • AB-INITIO

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