ePrints

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

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

Downloads

Full text for this publication is not currently held within this repository. Alternative links are provided below where available.

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

Altmetrics

Share