om200793p_si_002.cif (52.75 kB)
Enthalpy- vs Entropy-Driven Complexation of Homoallylic Alcohols by Rhodium(I) Complexes
dataset
posted on 2011-11-28, 00:00 authored by Sung Ok Kang, Vincent M. Lynch, Victor W. Day, Eric V. AnslynThe thermodynamics of binding between several homoallylic
alcohols
and simple olefinic Rh(I) compounds was examined with 1H NMR spectroscopy and isothermal titration calorimetry (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.
