Strength of Intramolecular Hydrogen Bonds

doi:10.3866/PKU.WHXB201708174

Abstract

Abstract:

The concept of resonance-assisted hydrogen bonds (RAHBs) highlights the synergistic interplay between the π-resonance and hydrogen bonding interactions. This concept has been well-accepted in academia and is widely used in practice. However, it has been argued that the seemingly enhanced intramolecular hydrogen bonding (IMHB) in unsaturated compounds may simply be a result of the constraints imposed by the σ-skeleton framework. Thus, it is crucial to estimate the strength of IMHBs. In this work, we used two approaches to probe the resonance effect and estimate the strength of the IMHBs in the two exemplary cases of the enol forms of acetylacetone and o-hydroxyacetophenone. One approach is the block-localized wavefunction (BLW) method, which is a variant of the ab initio valence bond (VB) theory. Using this approach, it is possible to derive the geometries and energetics with resonance shut down. The other approach is Edmiston's truncated localized molecular orbital (TLMO) technique, which monitors the energy changes by removing the delocalization tails from localized molecular orbitals. The integrated BLW and TLMO studies confirmed that the hydrogen bonding in these two molecules is indeed enhanced by π-resonance, and that this enhancement is not a result of σ constraints.

Key words: Resonance-assisted hydrogen bond, Bond strength, Valence bond, Block-localized wavefunction, Truncated localized molecular orbital

Xiaoyu JIANG,Wei WU,Yirong MO. Strength of Intramolecular Hydrogen Bonds[J]. Acta Phys. -Chim. Sin. 2018, 34(3), 278-285. doi: 10.3866/PKU.WHXB201708174

References

1	Scheiner S. Hydrogen Bonding: A Theoretical Perspective New York: Oxford University Press, 1997.
2	Jeffrey G. A. An Introduction to Hydrogen Bonding New York: Oxford University Press, 1997.
3	Desiraju G. R. ; Steiner T. The Weak Hydrogen Bond In Structural Chemistry and Biology New York: Oxford University Press, 2001.
4	Hydrogen Bonding -New Insights; Grabowski, S. J., Ed. ; Springer: Berlin, 2006; Vol. 3.
5	Gilli, G.; Gilli, P. The Nature of the Hydrogen Bond: Outline of a Comprehensive Hydrogen Bond Theory; Oxford University Press: New York, 2009; Vol.23.
6	Supramolecular Assembly via Hydrogen Bonds; Mingos, D. M. P. Ed. ; Springer: Berlin, 2010; Vol. 108.
7	Gilli G. ; Bellucci F. ; Ferretti V. ; Bertolasi V. J. Am. Chem. Soc. 1989, 111, 1023.
8	Bertolasi V. ; Gilli P. ; Ferretti V. ; Gilli G. J. Am. Chem. Soc. 1991, 113, 4917.
9	Gilli P. ; Bertolasi V. ; Ferretti V. ; Gilli G. J. Am. Chem. Soc. 2000, 122, 10405.
10	Gilli P. ; Bertolasi V. ; Pretto L. ; Ly?ka A. ; Gilli G. J. Am. Chem. Soc. 2002, 124, 13554.
11	Gilli P. ; Bertolasi V. ; Pretto L. ; Ferretti V. ; Gilli G. J. Am. Chem. Soc. 2004, 126, 3845.
12	Srinivasan R. ; Feenstra J. S. ; Park S. T. ; Xu S. ; Zewail A. H. J. Am. Chem. Soc. 2004, 126, 2266.
13	Sobczyk L. ; Grabowski S. J. ; Krygowski T. M. Chem. Rev. 2005, 105, 3513.
14	Sanz P. ; Mó O. ; Yá?ez M. ; Elguero J. J. Phys. Chem. A 2007, 111, 3585.
15	Sanz P. ; Mó O. ; Yá?ez M. ; Elguero J. Chem. Eur. J. 2008, 14, 4225.
16	Alkorta I. ; Elguero J. ; Mó O. ; Yá?ez M. ; Del Bene J. E. Mol. Phys. 2004, 102, 2563.
17	Alkorta I. ; Elguero J. ; Mó O. ; Yá?ez M. ; Del Bene J. E. Chem. Phys. Lett. 2005, 411, 411.
18	Beck J. F. ; Mo Y. J. Comput. Chem. 2007, 28, 455.
19	Grabowski S. J. J. Phys. Org. Chem. 2003, 16, 797.
20	Grabowski S. J. J. Mol. Struct. 2001, 562, 137.
21	Grabowski S. J. J. Phys. Chem. A 2001, 105, 10739.
22	Grabowski S. J. J. Phys. Org. Chem. 2004, 17, 18.
23	Wang C. S. ; Zhang Y. ; Gao K. ; Yang Z. Z. J. Chem. Phys. Chem. A 2005, 123, 024307.
24	Jablonski M. ; Kaczmarek A. ; Sadlej A. J. J. Phys. Chem. A 2006, 110, 10890.
25	Liu T. ; Li H. ; Huang M. B. ; Duan Y. ; Wang Z. X. J. Phys. Chem. A 2008, 112, 5436.
26	Deshmukh M. M. ; Gadre S. R. J. Phys. Chem. A 2009, 113, 7927.
27	Gilli P. ; Pretto L. ; Bertolasi V. ; Gilli G. Acc. Chem. Res. 2009, 42, 33.
28	Wendler K. ; Thar J. ; Zahn S. ; Kirchner B. J. Phys. Chem. A 2010, 114, 9529.
29	Valence Bond Theory; Cooper, D. L. Ed.;Amsterdam:Elsevier2002.
30	Gallup G. A. Valence Bond Methods: Theory and Applications New York: Cambridge University Press, 2002.
31	ShaikS. S.;HibertyP. C.A Chemist's Guide to Valence Bond Theory;Wiley:Hoboken, New Jersey2008.
32	Wu W. ; Su P. ; Shaik S. ; Hiberty P. C. Chem. Rev. 2011, 111, 7557.
33	Mo Y. ; Peyerimhoff S. D. J. Chem. Phys. Chem. A 1998, 109, 1687.
34	Mo Y. ; Song L. ; Lin Y. J. Phys. Chem. A 2007, 111, 8291.
35	Mo Y. In The Chemical Bond: Fundamental Aspects of Chemical Bonding; Frenking, G., Shaik, S., Eds. ; Wiley-VCH: Weinheim, Germany, 2014, p 199.
36	Rozas I. Phys. Chem. Chem. Phys. 2007, 9, 2782.
37	Estácio S. G. ; Cabral do Couto P. ; Costa Cabral B. J. ; Minas da Piedade M. E. ; Martinho Sim es J. A. J. Phys. Chem. A 2004, 108, 10834.
38	Lipkowskia P. ; Kolla A. ; Karpfenb A. ; Wolschannb P. Chem. Phys. Lett. 2002, 360, 256.
39	Woodford J. N. J. Phys. Chem. A 2007, 111, 8519.
40	Latajka Z. ; Scheiner S. J. Phys. Chem. 1994, 96, 9764.
41	Scheiner S. ; Kar T. ; ?uma M. J. Phys. Chem. A 1997, 101, 5901.
42	González L. ; Mó O. ; Yá?ez M. J. Phys. Chem. A 1997, 101, 9710.
43	Zhang Y. ; Wang C. S. J. Comput. Chem. 2009, 30, 1251.
44	Rozas I. ; Alkorta I. ; Elguero J. J. Phys. Chem. A 2001, 105, 10462.
45	Deshmukh M. M. ; Gadre S. R. ; Bartolotti L. J. J. Phys. Chem. A 2006, 110, 12519.
46	Bader R. F. W. Atoms in Molecules: A Quantum Theory Oxford U. K.: Oxford University Pres.
47	Pacios L. F. J. Phys. Chem. A 2004, 108, 1177.
48	LaPointe S. M. ; Farrag S. ; Bohrquez H. J. ; Boyd R. J. J. Phys. Chem. B 2009, 113, 10957.
49	Mo Y. J. Phys. Chem. A 2012, 116, 5240.
50	Reed A. E. ; Curtiss L. A. ; Weinhold F. Chem. Rev. 1988, 88, 899.
51	Weinhold F. ; Landis C. Valency and Bonding Cambridge, England: Cambridge University Press.
52	Pophristic V. ; Goodman L. Nature 2001, 411, 565.
53	Bickelhaupt F. M. ; Baerends E. J. Angew. Chem. Int. Ed. 2003, 42, 4183.
54	Weinhold F. Angew. Chem. Int. Ed. 2003, 42, 4188.
55	Mo Y. ; Gao J. Acc. Chem. Res. 2007, 40, 113.
56	Mo Y. ; Wu W. ; Song L. ; Lin M. ; Zhang Q. ; Gao J. Angew. Chem. Int. Ed. 2004, 43, 1986.
57	Edmiston C. Theochem 1988, 46, 331.
58	Mo Y. ; Zhang Q. J. Mol. Struct.(Theochem) 1995, 357, 171.
59	Song L. ; Mo Y. ; Zhang Q. ; Wu W. J. Comput. Chem. 2005, 26, 514.
60	SongL.;ChenZ.;YingF.;SongJ.;ChenX.;SuP.;MoY.;ZhangQ.;WuW.XMVB 2. 0: An ab initio Non-orthogonal Valence Bond Program;Xiamen:Xiamen University2012.
61	Mulliken R. S. ; Parr R. G. J. Chem. Phys. Chem. A 1951, 19, 1271.
62	Sovers O. J. ; Kern C. W. ; Pitzer R. M. ; Karplus M. J. Chem. Phys. Chem. A 1968, 49, 2592.
63	Stoll H. ; Preuss H. Theor. Chim. Acta 1977, 46, 11.
64	Kollmar H. J. Am. Chem. Soc. 1979, 101, 4832.
65	Mehler E. L. J. Chem. Phys. Chem. A 1977, 67, 2728.
66	Gianinetti E. ; Raimondi; Tornaghi E. Int. J. Quantum Chem. 1996, 60, 157.
67	Mo Y. J. Chem. Phys. Chem. A 2003, 119, 1300.
68	Schmidt M. W. ; Baldridge K. K. ; Boatz J. A. ; Elbert S. T. ; Gordon M. S. ; Jensen J. J. ; Koseki S. ; Matsunaga N. ; Nguyen K. A. ; Su S. ; Windus T. L. ; Dupuis M. ; Montgomery J. A. J. Comput. Chem. 1993, 14, 1347.
69	Andersson M. P. ; Uvdal P. J. Phys. Chem. A 2005, 109, 2937.
70	Boys S. F. Rev. Mod. Phys. 1960, 32, 296.
71	Edmiston C. ; Ruedenberg K. Rev. Mod. Phys. 1963, 35, 457.
72	Pipek J. ; Mezey P. G. J. Chem. Phys. Chem. A 1989, 90, 4916.
73	Ichikawa M. Acta Cryst. 1978, B34, 2074.
74	Steiner T. ; Saenger W. Acta Cryst. 1994, B50, 348.
75	Mo Y. ; Gao J. ; Peyerimhoff S. D. J. Chem. Phys. Chem. A 2000, 112, 5530.
76	Mo Y. ; Bao P. ; Gao J. Phys. Chem. Chem. Phys. 2011, 13, 6760.
77	Mó O. ; Yánez M. ; Elguero J. J. Chem. Phys. Chem. A 1992, 97, 6628.
78	Espinosa E. ; Molins E. ; Lecomte C. Chem. Phys. Lett. 1998, 285, 170.
79	Espinosa E. ; Molins E. J. Chem. Phys. Chem. A 2000, 113, 5686.
80	Koch U. ; Popelier P. L. A. J. Phys. Chem. A 1995, 99, 9747.
81	Popelier P. L. A. J. Phys. Chem. A 1998, 102, 1873.

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