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. 

LanguageEnglish
Pages283-289
Number of pages7
JournalJournal of Organometallic Chemistry
Volume572
Issue number2
DOIs
Publication statusPublished - 15 Jan 1999

Fingerprint

Lithium
Amides
Pyridine
amides
pyridines
lithium
Orbital calculations
crowding
Coordination Complexes
X ray analysis
Molecular orbitals
synthesis
Metal complexes
metals
molecular orbitals
Stabilization
stabilization
Metals
X-Rays
Single crystals

Keywords

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

Cite this

Clegg, W ; Liddle, S T ; Henderson, K W ; Keenan, F E ; Kennedy, A R ; McKeown, A E ; Mulvey, R E . / Synthesis, characterisation and a theoretical investigation of the formation of lithium dialkylaluminium amides. In: Journal of Organometallic Chemistry. 1999 ; Vol. 572, No. 2. pp. 283-289.
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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. ",
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Synthesis, characterisation and a theoretical investigation of the formation of lithium dialkylaluminium amides. / Clegg, W ; Liddle, S T ; Henderson, K W ; Keenan, F E ; Kennedy, A R ; McKeown, A E ; Mulvey, R E .

In: Journal of Organometallic Chemistry, Vol. 572, No. 2, 15.01.1999, p. 283-289.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Synthesis, characterisation and a theoretical investigation of the formation of lithium dialkylaluminium amides

AU - Clegg, W

AU - Liddle, S T

AU - Henderson, K W

AU - Keenan, F E

AU - Kennedy, A R

AU - McKeown, A E

AU - Mulvey, R E

PY - 1999/1/15

Y1 - 1999/1/15

N2 - 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. 

AB - 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. 

KW - lithium

KW - aluminium

KW - alkyls

KW - amides

KW - molecular orbital calculations

KW - trimeric dibenzylamidolithium

KW - diethyl-ether

KW - solid-state

KW - complexes

KW - alkyl

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DO - 10.1016/S0022-328X(98)00954-1

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T2 - Journal of Organometallic Chemistry

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