The nature of the hydrogen bond : outline of a comprehensive hydrogen bond theory / Gastone Gilli and Paola Gilli.

Format:

Book

Author/Creator:

Gilli, Gastone.

Contributor:

Gilli, Paola.

Series:

International Union of Crystallography monographs on crystallography ; 23.

IUCr monographs on crystallography ; 23

Language:

English

Subjects (All):

Hydrogen bonding.

Physical Description:

1 online resource (336 p.)

Place of Publication:

Oxford ; New York : Oxford University Press, 2009.

Language Note:

English

Summary:

Hydrogen bond (H-bond) effects are known: it makes sea water liquid, joins cellulose microfibrils in trees, shapes DNA into genes and polypeptide chains into wool, hair, muscles or enzymes. Its true nature is less known and we may still wonder why O-H...O bond energies range from less than 1 to more than 30 kcal/mol without apparent reason. This H-bond puzzle is re-examined here from its very beginning and presented as an inclusive compilation of experimental H-bond energies andgeometries.New concepts emerge from this analysis: new classes of systematically strong H-bonds (CAHBs and RAHBs: cha

Contents:

Contents; Introduction; 1 A century of the hydrogen bond (H-bond); 1.1 The discovery of the H-bond; 1.2 The theoretical understanding of the H-bond; 1.3 The experimental approach to the H-bond; 1.4 Significant books and reviews; 2 Generalities, definitions and preliminary classification; 2.1 Basic H-bond nomenclature; 2.2 Formal H-bond definitions; 2.3 The H-bond as a shared-proton interaction: A chemical classification; 2.4 H-bonds involving main-group elements (Class 1); 2.4.1 Conventional H-bonds (Group 1.1); 2.4.2 Weak H-bonds: General properties (Groups 1.2-4)

2.4.3 Weak H-bond donors (Group 1.2)2.4.4 Weak H-bond acceptors (Group 1.3); 2.4.5 Weak π-acceptors (Group 1.4); 2.5 H-bonds involving metal centers (Class 2); 2.5.1 Metals as H-bond donors (Group 2.1); 2.5.2 Metals as H-bond acceptors (Group 2.2); 2.5.3 Metal hydrides as H-bond acceptors or dihydrogen bond (DHB) (Group 2.3); 2.5.4 Metal ligands as H-bond donors or acceptors (Groups 2.4-5); 2.6 H-bond classification by physical properties: Weak, moderate, and strong H-bonds; 2.7 Correlation among physical descriptors: The problem of the driving variable

3 Modelling the H-bond by crystallographic methods3.1 Crystallographic databases and structural correlations; 3.1.1 A survey of structural databases; 3.1.2 Crystal-structure correlation (CSC) methods; 3.1.3 Bond lengths, bond energies and bond-number conservation rule; 3.2 A new class of H-bonds: The resonance-assisted H-bond (RAHB); 3.2.1 Cooperative H-bonds: An introduction; 3.2.2 Evidence for RAHB from CSC studies of ß-diketone enols; 3.2.3 RAHB generalization and systematics; 3.3 Completing the H-bond classification: The chemical leitmotifs

3.3.1 A full H-bond classification from the systematic analysis of the O-H···O system3.3.2 CAHB generalization to other homonuclear X-H···X bonds; 3.3.3 CAHB generalization to heteronuclear X-H···Y bonds; 3.3.4 CAHB geometry-energy relationships; 4 Modelling the H-bond by thermodynamic methods; 4.1 Introduction; 4.2 The use of ΔPA and ΔpK[sub(a)] indicators in H-bond studies; 4.2.1 PA and pK[sub(a)] definitions; 4.2.2 Proton-transfer and proton-sharing H-bonds; 4.2.3 Computing ΔPA and ΔpK[sub(a)] values: The problem of ΔPA evaluation

4.2.4 The use of PA and pK[sub(a)] as predictors of the H-bond strength: A summary4.3 Predicting (-)CAHB and (+)CAHB strengths from enthalpy versus proton affinity correlations; 4.3.1 ΔH[sup(°)sub(DIS)] against ΔPA correlations; 4.3.2 A verification of the PA equalization principle; 4.4 Predicting H-bond strengths from crystal geometry versus pK[sub(a)] correlations; 4.4.1 pK[sub(a)] tables for the most common H-bond donors and acceptors; 4.4.2 The pK[sub(a)] slide rule; 4.4.3 Two projects for validating the pK[sub(a)] equalization principle

4.5 Appendix. pK[sub(a)] tables arranged for chemical functionality

Notes:

Description based upon print version of record.

Includes bibliographical references (p. [277]-313) and index.

Description based on print version record.

Description based on publisher supplied metadata and other sources.

ISBN:

0-19-158027-9

0-19-967347-0

1-282-36592-4

0-19-156792-2

9786612365928

OCLC:

495092295