A Structural and Theoretical Study of the Thiophosphinite and Dithiophosphinate Anions |
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| Authors: | Natalie E Mansfield Martyn P Coles Peter B Hitchcock |
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| Institution: | Department of Chemistry , University of Sussex , Falmer , Brighton , UK |
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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. |
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| Keywords: | Coordination compound crystal structure dithiophosphinate DFT lithium thiophosphinite |
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