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Hypervalent Sulfur-Functionalized Diphosphagermylene and Diphosphastannylene Compounds

Lookup NU author(s): Dr Keith Izod, Dr Ewan Clark, Professor William Clegg, Dr Ross Harrington

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Abstract

The reaction between either GeCl2(1,4-dioxane) or SnCl2 and 2 equiv of the lithium phosphide [{(Me3Si)(2)CH}P(C6H4-2-SMe)]Li(tmeda) gives the corresponding diphosphatetrylenes [{(Me3Si)(2)CH}P(C6H4-2-SMe)}(2)E [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 {(Me3Si)(2)CH}(C6H4-2-SMe)P-P(C6H4-2-SMe){CH(SiMe3)(2)} (14) as the major product.

Publication metadata

Author(s): Izod K, Clark ER, Clegg W, Harrington RW

Publication type: Article

Publication status: Published

Journal: Organometallics

Year: 2012

Volume: 31

Issue: 1

Pages: 246-255

Print publication date: 07/12/2011

ISSN (print): 0276-7333

ISSN (electronic): 1520-6041

Publisher: American Chemical Society

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

DOI: 10.1021/om2008327

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