Issue 23, 2000
From the journal:

Journal of the Chemical Society, Dalton Transactions

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

Kenneth W. Henderson,*a   Alan R. Kennedy,a   Arlene E. McKeowna  and  Diane Strachana  

* Corresponding authors

a Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, UK
E-mail: k.w.henderson@strath.ac.uk

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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Article information

DOI
https://doi.org/10.1039/B007038F
Article type
Paper
Submitted
30 Aug 2000
Accepted
20 Oct 2000
First published
16 Nov 2000

J. Chem. Soc., Dalton Trans., 2000, 4348-4353

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

K. W. Henderson, A. R. Kennedy, A. E. McKeown and D. Strachan, J. Chem. Soc., Dalton Trans., 2000, 4348 DOI: 10.1039/B007038F

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