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 language | English |
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Pages (from-to) | 4348-4353 |
Number of pages | 5 |
Journal | Journal of the Chemical Society, Dalton Transactions |
Volume | 2000 |
Issue number | 23 |
DOIs | |
Publication status | Published - 16 Nov 2000 |
Keywords
- phosphonates
- molar crystallographic
- molecular channels
- chelation
- nitrile unit