Synthesis, characterisation and a theoretical investigation of the formation of lithium dialkylaluminium amides

W Clegg, S T Liddle, K W Henderson, F E Keenan, A R Kennedy, A E McKeown, R E Mulvey

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

Reaction of the pre-formed crystalline amides [(PhCH2)(2)NLi] and [Me2AlN(CH2Ph)(2)] in the presence of pyridine results in the formation of the mixed metal complex [Me2Al{(PhCH2)(2)N}(2)Li . pyr] 1. Ab initio molecular orbital calculations indicate formation of the bimetallic product is energetically favourable. Using single crystal X-ray analysis for 1 and the pyridine solvate [{(PhCH2)(2)NLi . pyr}(2)] 7, in combination with theoretical calculations, the possible driving forces for the reaction are discussed. A major contributing factor in the stabilisation of the bimetallic compound was found to be a reduction in steric crowding in the mixed metal base compared to the homometallic dialkylaluminium amide. In addition, complex 1 shows significant benzyl to lithium interactions which contribute to the overall bonding. Such interactions are unusual in that donor solvent is present as competing complexant. 

Original languageEnglish
Pages (from-to)283-289
Number of pages7
JournalJournal of Organometallic Chemistry
Volume572
Issue number2
DOIs
Publication statusPublished - 15 Jan 1999

Keywords

  • lithium
  • aluminium
  • alkyls
  • amides
  • molecular orbital calculations
  • trimeric dibenzylamidolithium
  • diethyl-ether
  • solid-state
  • complexes
  • alkyl

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