Toggle Main Menu Toggle Search

Open Access padlockePrints

Alkali metal complexes of a naphthylamine-substituted phosphanide

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


Publication metadata

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


Altmetrics

Altmetrics provided by Altmetric


Actions

Find at Newcastle University icon    Link to this publication


Share