Hypervalent sulfur-functionalized diphosphagermylene and diphosphastannylene compounds

Izod, Keith, Clark, Ewan R., Clegg, William, Harrington, Ross W. (2012) Hypervalent sulfur-functionalized diphosphagermylene and diphosphastannylene compounds. Organometallics, 31 (1). pp. 246-255. ISSN 0276-7333. (doi:10.1021/om2008327) (The full text of this publication is not currently available from this repository. You may be able to access a copy if URLs are provided)

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http://www.dx.doi.org/10.1021/om2008327

Abstract

The reaction between either GeCl 2(1,4-dioxane) or SnCl 2 and 2 equiv of the lithium phosphide [{(Me 3Si) 2CH}P(C 6H 4-2-SMe)]Li(tmeda) gives the corresponding diphosphatetrylenes [{(Me 3Si) 2CH}P(C 6H 4-2-SMe)] 2E [E = Ge (10), Sn (11)] in good yields. Both 10 and 11 crystallize as discrete monomers in which the Ge and Sn atoms are coordinated by both P and S atoms. Although 10 and 11 crystallize as racemic mixtures of the RR and SS diastereomers, variable-temperature NMR experiments suggest that, in solution, these compounds are in dynamic equilibrium with small amounts of the corresponding RS and SR diastereomers. DFT calculations reveal that the lowest-energy minima for both 10 and 11 possess rac stereochemistry; two higher-energy minima were located for each of 10 and 11, both of which have meso stereochemistry. The two calculated meso diastereomers differ in the location of the sulfur and phosphorus substituents within the pseudo-trigonalbipyramidal structures. Both 10 and 11 decompose on exposure to light, generating the diphosphine {(Me 3Si) 2CH}(C 6H 4-2-SMe)P-P(C 6H 4-2-SMe){CH(SiMe 3) 2} (14) as the major product. © 2011 American Chemical Society.

Item Type: Article
DOI/Identification number: 10.1021/om2008327
Uncontrolled keywords: 1 ,4-Dioxane, DFT calculation, Diastereomers, Diphosphines, Dynamic equilibria, Good yield, Lithium phosphide, Racemic mixtures, Variable-temperature NMR, Density functional theory, Ethers, Germanium, Lithium, Nuclear magnetic resonance spectroscopy, Phosphorus, Silicon, Stereochemistry, Stereoselectivity, Sulfur, Tin, Lithium compounds
Subjects: Q Science > QD Chemistry
Divisions: Faculties > Sciences > School of Physical Sciences > Functional Materials Group
Depositing User: Giles Tarver
Date Deposited: 29 Jul 2015 15:15 UTC
Last Modified: 29 May 2019 14:56 UTC
Resource URI: https://kar.kent.ac.uk/id/eprint/49879 (The current URI for this page, for reference purposes)
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