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Experimental and Computational Insights into the Stabilization of Low-Valent Main Group Elements Using Crown Ethers and Related Ligands
Journal of the American Chemical Society (2012)
  • Charles L. B. Macdonald, University of Windsor
  • Rajoshree Bandyopadhyay, University of Windsor
  • Benjamin F. T. Cooper, University of Windsor
  • Warren W. Friedl, University of Windsor
  • Aaron J. Rossini, University of Windsor
  • Robert W. Schurko, University of Windsor
  • S. Holger Eichhorn, University of Windsor
  • Rolfe H. Herber, The Hebrew University of Jerusalem
Abstract
A series of tin(II) triflate and chloride salts in which the cations are complexed by either cyclic or acyclic polyether ligands and which have well-characterized single-crystal X-ray structures are investigated using a variety of experimental and computational techniques. Mössbauer spectroscopy illustrates that the triflate salts tend to have valence electrons with higher s-character, and solid-state NMR spectroscopy reveals marked differences between superficially similar triflate and chloride salts. Cyclic voltammetry investigations of the triflate salts corroborate the results of the Mössbauer and NMR spectroscopy and reveal substantial steric and electronic effects for the different polyether ligands. MP2 and DFT calculations provide insight into the effects of ligands and substituents on the stability and reactivity of the low-valent metal atom. Overall, the investigations reveal the existence of more substantial binding between tin and chlorine in comparison to the triflate substituent and provide a rationale for the considerably increased reactivity of the chloride salts.
Publication Date
January 31, 2012
DOI
10.1021/ja211135s
Publisher Statement
Reprinted (adapted) with permission from Journal of American Chemical Society, 134(9); 4332-4345. Doi: 10.1021/ja211135s. Copyright 2012 American Chemical Society.
Citation Information
Charles L. B. Macdonald, Rajoshree Bandyopadhyay, Benjamin F. T. Cooper, Warren W. Friedl, et al.. "Experimental and Computational Insights into the Stabilization of Low-Valent Main Group Elements Using Crown Ethers and Related Ligands" Journal of the American Chemical Society Vol. 134 Iss. 9 (2012) p. 4332 - 4345
Available at: http://works.bepress.com/aaron-rossini/20/