Methanediide formation via hydrogen elimination in magnesium versus aluminium hydride complexes of a sterically demanding bis(iminophosphoranyl)methanediide

Christian P. Sindlinger, Samuel R. Lawrence, David B. Cordes, Alexandra M. Z. Slawin, Andreas Stasch

Research output: Contribution to journalArticlepeer-review

3 Citations (Scopus)

Abstract

Substituted bis(iminophosphoranyl)methanes are CH acidic compounds that can form complexes with formally dianionic central carbon centres. The reaction of H2C(Ph2P=NDip)2 (≡ H2L), Dip = 2,6-diisopropylphenyl, with one equivalent of di-n-butylmagnesium afforded the methanide complex [HLMgnBu] 1. Treatment of complex 1 with phenylsilane in aromatic solvents at elevated temperatures afforded the methanediide complex [(LMg)2] 2 presumably via the MgH intermediate [(HLMgH)n] (n = 1 or 2). The reaction of 1 with LiAlH4 in diethyl ether yielded the AlH complex [HLAlH2] 3. Alternatively, this complex was also obtained from the reaction of H2L with AlH3∙NMe3. The molecular structures of [HLMgnBu] 1, [(LMg)2] 2, and [HLAlH2] 3 are reported. Complex 3 shows no sign of H2 elimination to a methanediide species at elevated temperatures in contrast to the facile elimination of the putative reaction intermediate [(HLMgH)n] (n = 1 or 2) to form [(LMg)2] 2. The chemical properties of complex 2 were investigated and this complex appears to be stable against coordination with strong donor molecules.
Original languageEnglish
JournalInorganics
Volume5
Issue number2
Early online date22 Apr 2017
DOIs
Publication statusPublished - Jun 2017

Keywords

  • Alane
  • Aluminium
  • Hydrogen formation
  • Magnesium
  • Magnesium hydride
  • Metal hydrides
  • Methanediides
  • N,N′-chelation

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