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Acyclic Dialkylstannylene and -Plumbylene Compounds That Are Monomeric in the Solid State

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

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Abstract

The new phosphine-borane adduct (Me2PhSi)CH2P(BH3)Me-2 is prepared by the reaction between Me2PhSiCl and in situ-gencrated Me2P(BH3)CH2Li; the adduct undergoes clean deprotonation on treatment with n-BuLi to give the phosphine-borane-stabilized carbanion complex [(Me2PhSi)-{Me2P(BH3)}CH]Li. The reaction between 2 equiv of [(Me2PhSi){Me2P(BH3)}CH]Li and either CP2Sn or CP2Pb gives the acyclic dialkylstannylene and -plumbylene compounds rac-[(Me2PhSi)-{Me2P(BH3))CH](2)E [E = Sn (13), Pb (14)]. Similarly, the reaction between 2 equiv Of [(Me3Si)-{Me2P(BH3)}CH]Li and either CP2Sn or CP2Pb yields rac-[(Me3Si){Me2P(BH3)}CH](2)E [E = Sn (15), Pb (16)]. X-ray crystallography reveals that compounds 13-16 crystallize as discrete monomers that are stabilized by two agostic-type B-H center dot center dot center dot E contacts in each case; multielement NMR spectroscopy and UV/visible spectroscopy indicate that these agostic-type contacts are preserved in solution. DFT calculations reveal that these B-H... E contacts stabilize compounds 13-16 by between 38.0 and 43.7 kcal mol(-1). Calculations suggest that the dimerization of 15, which is isoelectronic with the archetypal dialkylstannylene {(Me3Si)(2)CH}(2)Sn, to the corresponding distannene [(Me3Si){Me2P(BH3)}CH](2)Sn=Sn[CH{P(BH3)Me-2}(SiMe3)](2) (15(2)) is disfavored by some 30.5 kcal mol(-1.)


Publication metadata

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

Publication type: Article

Publication status: Published

Journal: Organometallics

Year: 2009

Volume: 28

Issue: 19

Pages: 5661-5668

ISSN (print): 0276-7333

ISSN (electronic): 1520-6041

Publisher: American Chemical Society

URL: http://dx.doi.org/10.1021/om900614q

DOI: 10.1021/om900614q


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