Chiral discrimination in hydrogen‐bonded complexes of butan‐2‐ol (m‐form) and hydrogen peroxide

A theoretical study was reported on the chiral discrimination of different chiral formers of hydrogen-bonded complexes of butan-2-ol (m-form of “ga,” “ag,” and “gg”) with hydrogen peroxide. This completes, together with previous results on the butan-2-ol (h-form)···HOOH complexes [Zhang et al., J Mol Struct (Theochem), 2008, 864, 56], the study of two forms of butan-2-ol: m-form and h-form. Altogether, 12 minimum structures were located, and they are bound by intermolecular hydrogen bonds. The largest chirodiastaltic energy of the two most stable complexes was found for (SM-2)-(SP-2) of “gg”, at −0.238 kcal mol−1 in favor of the SM-2 complex in the “gg” configuration. The largest diastereofacial energy was found for (SP-2)-SP of “ga,” at −3.763 kcal mol−1 in favor of the SP-2 complex in the “ga” configuration. Moreover, the diastereofacial interactions lead to a preference for the SM-2 and SP-2 over the SM and SP for all the butan-2-ol (m-form)···HOOH complexes. The values of the largest chirodiastaltic energy and diastereofacial energy are similar to butan-2-ol (h-form), but the sign of the value (diastereofacial energy) is reverse. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009

[1]  Dezhan Chen,et al.  Chiral discrimination in hydrogen-bonded complexes of butan-2-ol and hydrogen peroxide , 2008 .

[2]  Yunjie Xu,et al.  Molecular recognition in 1 : 1 hydrogen-bonded complexes of oxirane and trans-2,3-dimethyloxirane with ethanol: a rotational spectroscopic and ab initio study. , 2007, Physical chemistry chemical physics : PCCP.

[3]  Yunjie Xu,et al.  Chiral self-recognition: direct spectroscopic detection of the homochiral and heterochiral dimers of propylene oxide in the gas phase. , 2006, Journal of the American Chemical Society.

[4]  J. Elguero,et al.  Self-aggregation as a source of chiral discrimination , 2006 .

[5]  Zheng-yu Zhou,et al.  Chiral discrimination in hydrogen-bonded complexes of hydrogen peroxide with methyl hydroperoxide: Theoretical study , 2006 .

[6]  Yunjie Xu,et al.  Ab initio study of chiral recognition in the propylene imine.hydrogen peroxide complex. , 2005, Physical chemistry chemical physics : PCCP.

[7]  A. Fu,et al.  Chiral discrimination in the hydrogen bonding complexes of the R–OOH (R=H and CH3) dimer , 2004 .

[8]  J. Elguero,et al.  Discrimination of hydrogen-bonded complexes with axial chirality , 2002 .

[9]  B. Ault,et al.  Matrix Isolation and ab Initio Study of 1:1 Hydrogen-Bonded Complexes of H2O2 with HF, HCl, and HBr , 2002 .

[10]  Howard,et al.  A High-Resolution Microwave Study of the Conformations of Butan-2-ol in a Supersonic Expansion. , 2001, Journal of molecular spectroscopy.

[11]  H. Lüthi,et al.  Chiral discrimination in hydrogen-bonded complexes , 2000 .

[12]  Kwang Soo Kim,et al.  Molecular Clusters of pi-Systems: Theoretical Studies of Structures, Spectra, and Origin of Interaction Energies. , 2000, Chemical reviews.

[13]  G. P. Moss.  Basic terminology of stereochemistry (IUPAC Recommendations 1996) , 1996 .

[14]  D. Craig,et al.  Discriminating interactions between chiral molecules. , 1976, Topics in current chemistry.

[15]  S. F. Boys,et al.  The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors , 1970 .