Lithiated alpha-cyanophosphonates: self-assembly of two-dimensional molecular sheets composed of interconnected twenty-four membered rings

K.W. Henderson, A.R. Kennedy, A.E. McKeown, D. Strachan

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

Reaction of the phosphonates (RO)2P(O)CH2CN (R = Et I or PriII) with one molar equivalent of LiNPri2 in THF gave the metallated complexes [(RO)2P(O)CHCNLi·THF] (R = Et 1 or Pri2). Crystallographic analyses of them reveal that they form dimeric Li2(O=P)2 units, which further aggregate through inter-dimer association via the nitrile of the phosphonate to form cross-linked, polymeric network structures. These sheets align in the crystals to form a patchwork arrangement of molecular channels. The carbanionic centres of the phosphonates are devoid of Li-C contacts and almost perfectly planar. In solution, the dimeric units most likely remain intact but the nitrile is involved in chelation to a metal centre via intra-dimer association. Theoretical calculations show that chelation of the nitrile unit is a viable mode of bonding.
Original languageEnglish
Pages (from-to)4348-4353
Number of pages5
JournalJournal of the Chemical Society, Dalton Transactions
Volume2000
Issue number23
DOIs
Publication statusPublished - 16 Nov 2000

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Keywords

  • phosphonates
  • molar crystallographic
  • molecular channels
  • chelation
  • nitrile unit

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