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Synthesis and structural characterisation of alkali metal complexes of heteroatom-stabilised 1,4-and 1,6-dicarbanions

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

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Abstract

A straightforward Peterson olefination reaction between either [{(Me2PhSi)(3)C}Li(THF)] or in situ-generated [(Me3Si)(2){Ph2P(BH3)}CLi(THF)(n)] and paraformaldehyde gives the alkenes (Me2PhSi)(2)C=CH2 (1) and (Me3Si){Ph2P(BH3)}C=CH2 (2), respectively, in good yield. Ultrasonic treatment of 1 with lithium in THF yields the lithium complex [{(Me2PhSi)(2)C(CH2)}Li(THF)(n)](2) (3), which reacts in situ with one equivalent of KOBu in diethyl ether to give the potassium salt [{(Me2PhSi)(2)C(CH2)}K(THF)](2) (4). Similarly, ultrasonic treatment of 2 with lithium in THF yields the lithium complex [[{Ph2P(BH3)}(Me3Si)C(CH2)]Li(THF)(3)](2). 2THF (5). The bis(phosphine-borane) [(Me3Si){Me-2(H3B)P}CH(Me2Si)(CH2)](2) (6) may be prepared by the reaction of [Me2P(BH3)CH(SiMe3)]Li with half an equivalent of ClSiMe2CH2CH2SiMe2Cl in refluxing THE Metalation of 6 with two equivalents of MeLi in refluxing THF yields the lithium complex [[{Me2P(BH3)}(Me3Si)C{(SiMe2)-(CH2)}]Li(THF)(3)](2) (9), whereas metalation with two equivalents of MeK in cold diethyl ether yields the potassium complex [[{Me2P(BH3)}(Me3Si)C{(SiMe2)(CH2)}](2)K-2(THF)(4)](infinity) (10) after recrystallisation. X-Ray crystallography shows that, whereas the lithium complex 5 crystallises as a discrete molecular species, the potassium complexes 4 and 10 crystallise as sheet and chain polymers, respectively.


Publication metadata

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

Publication type: Article

Publication status: Published

Journal: Dalton Transactions

Year: 2009

Issue: 17

Pages: 3340-3347

Print publication date: 01/01/2009

ISSN (print): 1477-9234

ISSN (electronic): 1477-9226

Publisher: Dalton Transactions

URL: http://dx.doi.org/10.1039/b822054a

DOI: 10.1039/b822054a


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