| I highly recommend this book
anyone who is truly interested in the hydrogen bond. The title is
clearly meant to recall Pauling’s classic book, The Nature of the
Chemical Bond, in which he summarizes his work on chemical
the current book, the Gillis (father and daughter) summarize the work
they have published with their co-workers on the hydrogen bond. As
such, the current work differs from other recent books on hydrogen
bonds, such as that by Jeffrey, which I previously reviewed (J. Am.
Chem. Soc. 1998,
120, 5604), much as a paper in Accounts
Research differs from one in Chemical ReViews.
The book consists of eight chapters. The first, entitled “A century
of the hydrogen bond (H-bond),” is a concise, yet critical,
introduction and historical review of hydrogen bonding. The Gillis take
care to disabuse the reader of many popular fallacies about H-bonds
that pervade the literature. For example, Pauling’s suggestion that
H-bonds are electrostatic in nature was meant only to apply to weak
(not all) H-bonds. The second chapter deals with definitions,
generalities, and preliminary classification of H-bonds based upon the
work of others.
The third and longest chapter covers modeling the H-bond using
crystallography. Here, the authors’ considerable expertise in
crystallography and practical applications of crystallographic
databases plays a very important role. They show how careful
interpretation of judiciously chosen crystal structures can deepen
one’s understanding of H-bonding. Roughly two-thirds of this chapter
deals with resonance-assisted H-bonds (RAHBs), a class of H-bonding
that the Gillis have studied in great detail. These H-bonds can be
quite strong and, therefore, important to structure determination. This
chapter includes an extensive analysis of a subclass of RAHBs that
occurs in tautomers of β-diketones,
such as acetylacetone. It also
includes further classification of H-bonds, including charge-assisted
hydrogen bonds (CAHBs).
In the fourth chapter, the authors discuss modeling H-bonds from a
thermodynamic perspective. Detailed discussions of the effects
matching upon the strength of H-bonds, particularly in the cases of
CAHBs, are presented as ways of predicting H-bond strengths from
thermodynamic data. Included is a very useful “pKa
slide rule”. This is followed by a short chapter on “empirical laws
governing the H-bond”.
The sixth chapter, “Outline of a novel transition-state H-bond
theory (TSHBT),” includes analyses using valence-bond and density
functional theory, analyses of the potential surfaces–which generally
include double-well potentials–and the application of Marcus theory to
these surfaces. The seventh chapter, “The strength of the H-bond:
Definitions and thermodynamics,” covers the strength of H-bonds in
different phases and in aqueous solution. It includes a detailed
discussion of the principle of enthalpy/entropy compensation as applied
to the H-bond. Finally, in the last chapter, the Gillis discuss the
role of strong H-bonds in nature, e.g., the importance of H-bond
cooperativity in biochemistry, crystal packing, and water.
No book is perfect, including this one. Among the deficiencies are the
choice of an erroneous analysis of the gas-phase electron diffraction
of acetylacetoneswhich did not take the fraction of the sample that is
not in the enol form, resulting in the hydrogen atom involved in
H-bonding appearing to be considerably out of the molecular
planesinstead of what seems to be a more correct one (see Lowery et al.
J. Am. Chem. Soc.
93, 6399). The following topics are not discussed: (1) trans-H-bond
scalar J-coupling among the NMR methods used for studying H-bonds, (2)
the zero-point vibration’s effect upon the experimental structures
resulting from surfaces with a low energy barrier in a double-well
system; (3) the isotopic substitution method of studying double-well
potentials, and (4) the effects of H-bonding on vibrational spectra.
Because this book is essentially an overview of the authors’
contributions, less space is allotted to those of other groups.
However, this should be expected based on analogy to Pauling’s book.
Another problem is that color plates of some of the most important
figures, including the aforementioned “pKa
slide rule,” are inserted as a group after page 180, without any
explanation or notation in the Table of Contents.
This book should be required reading for biochemists, many of whom seem
to have only a superficial idea of what the hydrogen bond really is, as
well as for anyone who designs or interprets empirical models that need
to reproduce systems where H-bonding is important. On the whole, I
believe this book to be a valuable contribution to our understanding of
H-bonds. The Gillis should be commended for the considerable time and
effort that they must have spent on this endeavor.
J. Dannenberg, City
University of New York-Hunter
The Graduate School
© 2010 American