Chemical double mutant cycles for the quantification of cooperativity in H-bonded complexes

CAMARA-CAMPOS, Amaya, MUSUMECI, Daniele, HUNTER, Christopher A. and TUREGA, Simon (2009). Chemical double mutant cycles for the quantification of cooperativity in H-bonded complexes. Journal of the American Chemical Society, 131 (51), 18518-18524.

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Abstract

Chemical double mutant cycles have been used in conjunction with new H-bonding motifs for the quantification of chelate cooperativity in multiply H-bonded complexes. The double mutant cycle approach specifically deals with the effects of substituents, secondary interactions, and allosteric cooperativity on the free energy contributions from individual H-bond sites and allows dissection of the free energy contribution due to chelate cooperativity associated with the formation of intramolecular noncovalent interactions. Two different doubly H-bonded motifs were investigated in carbon tetrachloride, chloroform, 1,1,2,2-tetrachloroethane, and cyclohexane, and the results were similar in all cases, with effective molarities of 3−33 M for formation of intramolecular H-bonds. This corresponds to a free energy penalty of 3−9 kJ mol−1 for formation of a bimolecular complex in solution, which is consistent with previous estimates of 6 kJ mol−1. This result can be used in conjunction with the H-bond parameters, α and β, to make a reasonable estimate of the stability constant for formation of a multiply H-bonded complex between two perfectly complementary partners, or to place an upper limit on the stability constant expected for a less complementary system.

Item Type:	Article
Additional Information:	Publication Date (Web): November 30, 2009
Research Institute, Centre or Group - Does NOT include content added after October 2018:	Biomedical Research Centre
Identification Number:	https://doi.org/10.1021/ja9083495
Page Range:	18518-18524
Depositing User:	Jamie Young
Date Deposited:	30 Jun 2015 12:47
Last Modified:	18 Mar 2021 18:45
URI:	https://shura.shu.ac.uk/id/eprint/10022

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