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Alkali metal complexes of a phosphine-borane-stabilised carbanion: Influence of co-ligands on structure

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

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Abstract

The adducts [[(Me3Si)2{Me2P(BH 3)}C]K(L)n]m [L = THF, n = 0.5, m = ∞ (2a); L = tmeda (2b), pmdeta (2c), n = 1, m = 2] may be synthesised by treatment of solvent-free [[(Me3Si)2{Me2P(BH 3)}C]K]∞ (2) with the corresponding Lewis base (tmeda = N,N,N′,N′-tetramethylethylenediamine; pmdeta = N,N,N′,N″,N″-pentamethyldiethylenetriamine). X-Ray crystallography reveals that, whereas 2 crystallises with a complex 2-dimensional sheet structure, 2a crystallises as a ribbon-type one-dimensional polymer and both 2b and 2c crystallise as dimers. The corresponding complex with 12-crown-4, [K(12-crown-4)2][(Me3Si)2{Me 2P(BH3)}C] (2d) crystallises as a separated ion pair. The complexes [[(Me3Si)2{Me2P(BH 3)}C]M(pmdeta)]n [M = Na, n = 1 (6); M = Rb, n = 2 (7)] may be synthesised by treatment of [(Me3Si)2{Me 2P(BH3)}C]M with pmdeta. Whereas 6 crystallises as a discrete monomer, compound 7 crystallises as a dimer. Compounds 2, 2a-2d, 6, 7 and the corresponding caesium derivative [[(Me3Si) 2{Me2P(BH3)}C]Cs(pmdeta)]2 (5) provide an opportunity to consider the influence of the ionic radius of the metal and the nature of the co-ligands on the structures of alkali metal complexes of a phosphine-borane-stabilised carbanion. This journal is © The Royal Society of Chemistry.


Publication metadata

Author(s): Izod K, Wills C, Clegg W, Harrington RW

Publication type: Article

Publication status: Published

Journal: Dalton Transactions

Year: 2007

Issue: 33

Pages: 3669-3675

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/b708279g

DOI: 10.1039/b708279g


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