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Phosphorus, Sulfur, and Silicon and the Related Elements Volume 183, 2008 - Issue 11
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Original Articles

A Structural and Theoretical Study of the Thiophosphinite and Dithiophosphinate Anions

Natalie E. Mansfield Department of Chemistry, University of Sussex, Falmer, Brighton, UK
,
Martyn P. Coles Department of Chemistry, University of Sussex, Falmer, Brighton, UK
&
Peter B. Hitchcock Department of Chemistry, University of Sussex, Falmer, Brighton, UK
Pages 2685-2702 | Received 03 Sep 2007, Accepted 31 Jan 2008, Published online: 10 Oct 2008
 
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Abstract

Two novel lithium compounds containing either the phosphorus-chalcogenide anions [Ph 2 PS]− or [Cy 2 PS 2 ]− were isolated as decomposition products in the attempted formation of phospha(V)guanidinate anions. Lithium diphenylthiophosphinite was structurally characterized as the dimeric TMEDA adduct [Li(Ph 2 PS)(TMEDA)] 2 (1), in which a rare example of the κ 1 -S bonding mode was observed for the anion. The dicyclohexyldithiophosphinate anion was incorporated into an aggregated structure with molecular formula [Li 5 (Cy 2 PS 2 ) 4 (OH)] 2 (2). DFT calculations were performed on the isolated [R 2 PS]− and [R 2 PS 2 ]− anions (R = Ph, Cy), indicating delocalization of electron density into the P-S bonds for each model, in agreement with bond-lengths taken from crystallographic data.

Acknowledgments

The University of Sussex and the EPSRC are thanked for financial support.

Notes

aValues taken from compound 1

bvalues taken from Cp2Ti(Cy2PS)2, see Reference 9.

aValues taken from [Ph3Te][Ph2PS2], in which only weak secondary cation· anions interactions are present, see Reference 29

brange of values taken from compound 2.

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