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Lookup NU author(s): Dr Keith Izod, Dr Peter Evans, Emeritus Professor William McFarlane, Dr Paul Waddell
This is the authors' accepted manuscript of an article that has been published in its final definitive form by American Chemical Society, 2018.
For re-use rights please refer to the publisher's terms and conditions.
The alkyl-tethered alpha,omega-diphosphines (Dipp)PH(CH2)nPH(Dipp) (n = 1 (3H), 2 (4H), 3 (5H), 4 (6H), 5 (7H)) have been prepared in good yield and have been characterized by multi-nuclear NMR spectroscopy [Dipp = 2,6-iPr2C6H3]. Treatment of 3H with two equivalents of nBuLi and two equivalents of TMEDA gives the diphosphide complex [CH2{P(Dipp)}2]Li2(TMEDA)2 (3Lia), which crystallizes as discrete monomers which do not exhibit temperature-dependent NMR behavior. Treatment of 4H-7H with two equivalents of nBuLi in THF gives the diphosphides [[CH2{P(Dipp)}]2]2Li4(THF)2(OEt2)2 (4Li), [CH2{CH2P(Dipp)}2]Li2(THF)4 (5Li), [{CH2CH2P(Dipp)}2]Li2(THF)6 (6Li), and [CH2{CH2CH2P(Dipp)}2]2Li4(THF)6.PhMe (7Li) after crystallization. Compounds 4Li-7Li adopt either monomeric or dimeric structures in the solid state, depending on the length of the alkyl tether of the diphosphide ligand. In solution, compounds 4Li-7Li exhibit dynamic behavior: variable-temperature 31P{1H} and 7Li NMR spectroscopic studies indicate that this involves equilibria between monomeric and dimeric or higher oligomeric species, with the nature of the equilibrium again depending on the length of the alkyl tether of the diphosphide ligand. The reactions between 3Li, 6Li or 7Li and SnCl2 in THF give mixtures of products which could not be separated. In contrast, the reactions between 4Li or 5Li and one equivalent of SnCl2 give the dimeric P-heterocyclic stannylenes [{CH2P(Dipp)}2Sn]2 (4Sn) and [CH2{CH2P(Dipp)}2Sn]2.½THF (5Sn), respectively. While compound 5Sn is isolated exclusively as the cis isomer, 4Sn is isolated as a mixture of cis and trans isomers in an approximate 5:1 ratio. The solid state structures of trans-4Sn and cis-5Sn were obtained and multi-nuclear NMR spectroscopy indicates that the dimeric structures of these compounds are maintained in solution. Compounds 4Sn and 5Sn represent the first P-heterocyclic stannylene dimers to be structurally characterized.
Author(s): Izod K, Evans P, Horsley Downie T, McFarlane W, Waddell PG
Publication type: Article
Publication status: Published
Journal: Inorganic Chemistry
Year: 2018
Volume: 57
Issue: 23
Pages: 14733-14747
Print publication date: 03/12/2018
Online publication date: 13/11/2018
Acceptance date: 01/11/2018
Date deposited: 04/12/2018
ISSN (print): 0020-1669
ISSN (electronic): 1520-510X
Publisher: American Chemical Society
URL: https://doi.org/10.1021/acs.inorgchem.8b02510
DOI: 10.1021/acs.inorgchem.8b02510
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