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Influence of aromatic ring substituents and co-ligand on the binding mode of a phosphine-borane-stabilized carbanion; crystal structures of [[(Me3Si)2{Ph2P(BH3)}C]KLn]2[Ln = (OEt2)2, pmdeta; pmdeta = N,N,N′,N″,N″-pentamethyldiethylenetriamine]

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

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Abstract

The phosphine-borane adduct (Me3Si)2CHPPh2(BH3) (1) is readily prepared from the reaction between (Me3Si)2CHPCl2 and 2 equiv of PhMgBr in refluxing THF, followed by treatment with BH3·SMe2. The reaction between 1 and MeK in cold diethyl ether proceeds cleanly to give [[(Me3Si)2{Ph2P(BH3)}C]K] (2), which may be crystallized in the presence of pmdeta to give the corresponding adduct [[(Me3Si)2{Ph2P(BH3)}C]K(pmdeta)]2 (2a) [pmdeta = N,N,N′,N″,N″-pentamethyldiethylenetriamine]. Treatment of 1 with MeK, followed by crystallization from cold diethyl ether, gives [[(Me3Si)2{Ph2P(BH3)}C]K(OEt2)2]2 (2b). X-ray crystallography reveals that in both 2a and 2b the phosphine-borane-stabilized carbanion ligand binds to the metal centers via its BH3 hydrogen atoms; there are no short contacts between the potassium ions and the carbanion centers. In 2b the ligand also binds the potassium ion through an η5-aryl interaction; in 2a this contact is absent. © 2007 Elsevier B.V. All rights reserved.


Publication metadata

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

Publication type: Article

Publication status: Published

Journal: Journal of Organometallic Chemistry

Year: 2007

Volume: 692

Issue: 22

Pages: 5060-5064

ISSN (print): 0022-328X

ISSN (electronic): 1872-8561

Publisher: Elsevier

URL: http://dx.doi.org/10.1016/j.jorganchem.2007.07.040

DOI: 10.1016/j.jorganchem.2007.07.040


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