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Lookup NU author(s): Dr Keith Izod, John Stewart, Professor William Clegg, Dr Ross Harrington
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The reaction between {(Me3Si)2CH}PCl2 and one equivalent of [C10H6-8-NMe2]Li, followed by in situ reduction with LiAlH4, gives the secondary phosphane {(Me3Si)2CH}(C10H6-8-NMe 2)PH (1) in good yield as a colourless crystalline solid. Metalation of 1 with BunLi in diethyl ether gives the lithium phosphanide [{[{(Me3Si)2CH}(C10H6-8-NMe 2)P]Li}2(OEt2)] (2), which undergoes metathesis with either NaOBut or KOBut to give the heavier alkali metal derivatives [[{(Me3Si)2CH}(C10H 6-8-NMe2)P]Na(tmeda)] (3) and [[{(Me3Si) 2CH}(C10H6-8-NMe2)P]K(pmdeta)] (4), after recrystallisation in the presence of the corresponding amine co-ligand [tmeda = N,N,N′,N′-tetramethylethylenediamine, pmdeta = N,N,N′,N″,N″-pentamethyldiethylenetriamine]. Compounds 2-4 have been characterised by 1H, 13C{1H} and 31P{1H} NMR spectroscopy, elemental analyses and X-ray crystallography. Dinuclear 2 crystallises with the phosphanide ligands arranged in a head-to-head fashion and is subject to dynamic exchange in toluene solution; in contrast, compounds 3 and 4 crystallise as discrete monomers which exhibit no dynamic behaviour in solution. DFT calculations on the model compound [{[(Me)(C10H6-8-NMe2)P]Li} 2(OMe2)] (2a) indicate that the most stable head-to-head form is favoured by 15.0 kcal mol-1 over the corresponding head-to-tail form. This journal is © The Royal Society of Chemistry.
Author(s): Izod K, Stewart JC, Clegg W, Harrington RW
Publication type: Article
Publication status: Published
Journal: Dalton Transactions
Year: 2008
Issue: 3
Pages: 363-370
Print publication date: 01/01/2008
ISSN (print): 1477-9226
ISSN (electronic): 1477-9234
Publisher: Royal Society of Chemistry
URL: http://dx.doi.org/10.1039/b715145d
DOI: 10.1039/b715145d
PubMed id: 18411846
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