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Alkali metal complexes of sterically demanding amino-functionalised secondary phosphanide ligands

Lookup NU author(s): Dr Keith Izod, John Stewart, Emeritus Professor Bill Clegg, Dr Ross Harrington

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Abstract

The reaction between {(Me3Si)2CH}PCl2 (4) and one equivalent of either [C6H4-2-NMe2]Li or [2-C5H4N]ZnCl, followed by in situ reduction with LiAlH4 gives the secondary phosphanes {(Me3Si) 2CH}(C6H4-2-NMe2)PH (5) and {(Me3Si)2CH}(2-C5H4N)PH (6) in good yields as colourless oils. Metalation of 5 with BunLi in THF gives the lithium phosphanide [[{(Me3Si)2CH}(C6H 4-2-NMe2)P]Li(THF)2] (7), which undergoes metathesis with either NaOBut or KOBut to give the heavier alkali metal derivatives [[{(Me3Si)2CH}(C 6H4-2-NMe2)P]Na(tmeda)] (8) and [[{(Me 3Si)2CH}(C6H4-2-NMe 2)P]K(pmdeta)] (9) after recrystallisation in the presence of the corresponding amine co-ligand [tmeda = N,N,N′,N′- tetramethylethylenediamine, pmdeta = N,N,N′,N″,N″- pentamethyldiethylenetriamine]. The pyridyl-functionalised phosphane 6 undergoes deprotonation on treatment with BunLi to give a red oil corresponding to the lithium compound [{(Me3Si)2CH}(2- C5H4N)P]Li (10) which could not be crystallised. Treatment of this oil with NaOBut gives the sodium derivative [{[{(Me 3Si)2CH}(2-C5H4N)P]Na} 2·(Et2O)]2 (11), whilst treatment of 10 with KOBut, followed by recrystallisation in the presence of pmdeta gives the complex [[{(Me3Si)2CH}(2-C5H 4N)P]K(pmdeta)]2 (12). Compounds 5-12 have been characterised by 1H, 13C{1H} and 31P{1H} NMR spectroscopy and elemental analyses; compounds 7-9, 11 and 12 have additionally been characterised by X-ray crystallography. Compounds 7-9 crystallise as discrete monomers, whereas 11 crystallises as an unusual dimer of dimers and 12 crystallises as a dimer with bridging pyridyl-phosphanide ligands. © The Royal Society of Chemistry 2007.


Publication metadata

Author(s): Izod K, Stewart JC, Clegg W, Harrington RW

Publication type: Article

Publication status: Published

Journal: Dalton Transactions

Year: 2007

Issue: 2

Pages: 257-264

Date deposited: 05/07/2010

ISSN (print): 1477-9226

ISSN (electronic): 1477-9234

Publisher: Royal Society of Chemistry

URL: http://dx.doi.org/10.1039/b614373c

DOI: 10.1039/b614373c


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