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.
LanguageEnglish
Pages4348-4353
Number of pages5
JournalJournal of the Chemical Society, Dalton Transactions
Volume2000
Issue number23
DOIs
Publication statusPublished - 16 Nov 2000

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Organophosphonates
Nitriles
Self assembly
Chelation
Dimers
Association reactions
Contacts (fluid mechanics)
Metals
Crystals

Keywords

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

Cite this

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title = "Lithiated alpha-cyanophosphonates: self-assembly of two-dimensional molecular sheets composed of interconnected twenty-four membered rings",
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.",
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Lithiated alpha-cyanophosphonates: self-assembly of two-dimensional molecular sheets composed of interconnected twenty-four membered rings. / Henderson, K.W.; Kennedy, A.R.; McKeown, A.E.; Strachan, D.

In: Journal of the Chemical Society, Dalton Transactions, Vol. 2000, No. 23, 16.11.2000, p. 4348-4353.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Lithiated alpha-cyanophosphonates: self-assembly of two-dimensional molecular sheets composed of interconnected twenty-four membered rings

AU - Henderson, K.W.

AU - Kennedy, A.R.

AU - McKeown, A.E.

AU - Strachan, D.

PY - 2000/11/16

Y1 - 2000/11/16

N2 - 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.

AB - 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.

KW - phosphonates

KW - molar crystallographic

KW - molecular channels

KW - chelation

KW - nitrile unit

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DO - 10.1039/b007038f

M3 - Article

VL - 2000

SP - 4348

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JO - Journal of the Chemical Society, Dalton Transactions

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