Phosphine chalcogenide complexes of antimony(III) halides

Author:

Bamford Karlee L.1,Robertson Alasdair P.M.1,Jenkins Hilary A.2,Patrick Brian O.3,Burford Neil1

Affiliation:

1. Department of Chemistry, University of Victoria, P.O. Box 3065, Stn CSC, Victoria, BC V8W 3V6, Canada.

2. Department of Chemistry, McMaster University, Hamilton, ON L8S 4M1, Canada.

3. Department of Chemistry, University of British Columbia, Vancouver, BC V6T 1Z1, Canada.

Abstract

Three series of phosphine chalcogenide complexes of the antimony(III) halides SbX3 (X = F, Cl, Br, or I) have been synthesized and characterized by spectroscopic and crystallographic methods. Complexes of the generic formulae (Cy3PO)SbX3 (X = F (1a), Cl (1b), or Br (1c)), (Cy3PO)2SbX3 (X = F (2a), Cl (2b), or Br (2c)), and (Cy3PS)SbX3 (X = Cl (3b), Br (3c), or I (3d)) were synthesized via the treatment of solutions of SbX3 with OPCy3 and SPCy3, respectively. Derivatives of (Cy3PO)SbX3 were characterized by single crystal X-ray diffraction for 1a and 1b and crystallize as dimers through symmetry related intermolecular Sb–X interactions, providing the first structurally characterized examples of this class of complex. Derivatives of (Cy3PS)SbX3 (3b–3c) adopt analogous dimeric structures in the solid state. The solid-state structure of (Cy3PO)2SbCl3 (2b) is consistent with the previously reported structures of bis-phosphine oxide complexes of antimony(III), with a square pyramidal Sb center and cis-configured OPCy3 ligands. The phosphine chalcogenide complexes of SbX3 display configurations that are consistent with the perceived trans-labilizing properties of the ligands/substituents.

Publisher

Canadian Science Publishing

Subject

Organic Chemistry,General Chemistry,Catalysis

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