Complementary nature of hydrogen bond basicity and acidity scales from electrostatic and atoms in molecules properties

DFT calculations over 120 hydrogen bond bases/acids and their complexes with hydrogen fluoride/hydrogen cyanide have been performed. By using properties computed at the B3LYP/6-31+G(d,p) level of theory as predictors of ∑βH2/∑αH2 in multivariate analysis, the overall hydrogen bond scale can be regarded as a composite descriptor made of an electrostatic term (by using minimum/maximum electrostatic potential values on the 0.001 au isodensity contour surface of the isolated base/acid) and of an overlap term (by using energy density values calculated at the bond critical point of 1∶1 HF/NCH complexes). These models underline the complementarity between the two overall hydrogen bond scales, and, for the first time, make accurate predictions for multi-functional bases/acids.

[1]  R. Bader,et al.  Quantum topology of molecular charge distributions. III. The mechanics of an atom in a molecule , 1980 .

[2]  Hanno Essén,et al.  The characterization of atomic interactions , 1984 .

[3]  Olivier Lamarche,et al.  Atoms in molecules investigation of the pKHB basicity scale: electrostatic and covalent effects in hydrogen bonding , 2003 .

[4]  J. Pople,et al.  Self‐Consistent Molecular‐Orbital Methods. IX. An Extended Gaussian‐Type Basis for Molecular‐Orbital Studies of Organic Molecules , 1971 .

[5]  Michael H. Abraham,et al.  Hydrogen bonding: XVII. The characterisation of 24 gas-liquid chromatographic stationary phases studied by Poole and co-workers. including molten salts, and evaluation of solute-stationary phase interactions , 1991 .

[6]  A. J. Kirby,et al.  A mechanism for efficient proton-transfer catalysis. Intramolecular general acid catalysis of the hydrolysis of 1-arylethyl ethers of salicylic acid , 1999 .

[7]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[8]  A. Ivancich,et al.  A comparative study of conserved protein interactions of the primary electron donor in photosynthetic purple bacterial reaction centers , 1998, Photosynthesis Research.

[9]  Cheng Chang,et al.  Properties of atoms in molecules: atomic volumes , 1987 .

[10]  Mark S. Gordon,et al.  The isomers of silacyclopropane , 1980 .

[11]  Michael H. Abraham,et al.  Scales of solute hydrogen-bonding: their construction and application to physicochemical and biochemical processes , 2010 .

[12]  J. Murray,et al.  Correlations between the solvent hydrogen-bond-donating parameter .alpha. and the calculated molecular surface electrostatic potential , 1991 .

[13]  Paul von Ragué Schleyer,et al.  Studies of hydrogen-bonded complex formation with p-fluorophenol. V. Linear free energy relationships with OH reference acids , 1969 .

[14]  R. Taft,et al.  Effects of polar aprotic solvents on linear free-energy relations in hydrogen-bonded complex formation , 1972 .

[15]  S. Ranganathan,et al.  Correlations between the solvent hydrogen bond acceptor parameter β and the calculated molecular electrostatic potential , 1991 .

[16]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[17]  D. Cremer,et al.  Theoretical determination of molecular structure and conformation. 15. Three-membered rings: bent bonds, ring strain, and surface delocalization , 1985 .

[18]  H. Hagelin,et al.  Family-independent relationships between computed molecular surface quantities and solute hydrogen bond acidity/basicity and solute-induced methanol O–H infrared frequency shifts , 1995 .

[19]  Richard F. W. Bader.  A quantum theory of molecular structure and its applications , 1991 .

[20]  T. Lectka,et al.  INTRAMOLECULAR CATALYSIS OF AMIDE ISOMERIZATION : KINETIC CONSEQUENCES OF THE 5-NH- -NA HYDROGEN BOND IN PROLYL PEPTIDES , 1998 .

[21]  G. Proctor,et al.  Bridged-ring nitrogen compounds. Part 7. Synthesis of the 1,4-ethano-3-benzazepine ring system , 1981 .

[22]  James A. Platts,et al.  Estimation of Molecular Linear Free Energy Relation Descriptors Using a Group Contribution Approach , 1999, J. Chem. Inf. Comput. Sci..

[23]  D. Gurka,et al.  Studies of hydrogen-bonded complex formation with p-fluorophenol. IV. Fluorine nuclear magnetic resonance method , 1969 .