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Enthalpy vs Entropy Driven Complexation of Homoallylic Alcohols by Rh(I) Complexes
Kang, Sung Ok Lynch, Vincent M. Day, Victor W. Anslyn, Eric V.
Kang, Sung Ok
Lynch, Vincent M.
Day, Victor W.
Anslyn, Eric V.
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Abstract
The thermodynamics of binding between several homoallylic alcohols and simple olefinic Rh(I) compounds was examined with 1H NMR spectroscopy and ITC. 1H NMR titrations revealed moderate binding of these alcohols with [Rh(COD)2]+ (1) and [Rh(COD)(CH3CN)2]+ (3), but weaker binding with [Rh(NBD)2]+ (2). ITC indicated that the complexation with [Rh(COD)2]+ is mainly governed by enthalpy whereas binding with [Rh(COD)(CH3CN)2]+ is entirely driven by entropy. The thermodynamic parameters for the homoallylic alcohol binding of Rh(I) complexes 1–3 are consistent with crystallographic data.
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This document is the Accepted Manuscript version of a Published Work that appeared in final form inOrganometallics, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://doi.org/10.1021/om200793p.
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2011-10-25
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American Chemical Society
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Day_2011.pdf
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Kang, S. O., Lynch, V. M., Day, V. W., & Anslyn, E. V. (2011). Enthalpy vs Entropy Driven Complexation of Homoallylic Alcohols by Rh(I) Complexes. Organometallics, 30(22), 6233–6240. http://doi.org/10.1021/om200793p