PHYSICAL INORGANICCHEMISTRY

PHYSICAL INORGANICCHEMISTRY

Principles, Methods, and Models

Edited by

Andreja Bakac

Copyright � 2010 by John Wiley & Sons, Inc. All rights reserved.

Published by John Wiley & Sons, Inc., Hoboken, New Jersey

Published simultaneously in Canada

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Library of Congress Cataloging-in-Publication Data:

Physical inorganic chemistry : principles, methods, and models / [edited by]

Andreja Bakac.

p. cm.

Includes index.

ISBN 978-0-470-22419-9 (cloth)

1. Physical inorganic chemistry. I. Bakac, Andreja.

QD475.P49 2010

547’.13–dc22 2009051003

Printed in the United States of America

10 9 8 7 6 5 4 3 2 1

To Jojika

CONTENTS

Preface ix

Contributors xi

1 Inorganic and Bioinorganic Spectroscopy 1

Edward I. Solomon and Caleb B. Bell III

2 57Fe M€ossbauer Spectroscopy in Chemistry and Biology 39

Marl�ene Martinho and Eckard M€unck

3 Magnetochemical Methods and Models in Inorganic Chemistry 69

Paul K€ogerler

4 Cryoradiolysis as a Method for Mechanistic Studies in Inorganic

Biochemistry 109

Ilia G. Denisov

5 Absolute Chiral Structures of Inorganic Compounds 143

James P. Riehl and Sumio Kaizaki

6 Flash Photolysis and Chemistry of Transients and Excited States 199

Guillermo Ferraudi

7 Application of High Pressure in the Elucidation of Inorganic

and Bioinorganic Reaction Mechanisms 269

Colin D. Hubbard and Rudi van Eldik

8 Chemical Kinetics as a Mechanistic Tool 367

Andreja Bakac

9 HeavyAtomIsotopeEffects asProbes ofSmallMoleculeActivation 425

Justine P. Roth

10 ComputationalStudiesofReactivity inTransitionMetalChemistry 459

Jeremy N. Harvey

Index 501

vii

PREFACE

Physical inorganic chemistry is an enormous area of science. In the broadest sense, it

comprises experimental and theoretical approaches to the thermodynamics, kinetics,

and structure of inorganic compounds and their chemical transformations in solid,

gas, and liquid phases. When I accepted the challenge to edit a book on this broad

topic, it was clear that only a small portion of the field could be covered in a project of

manageable size. The result is a text that focuses on mechanistic aspects of inorganic

chemistry in solution, similar to the frequent association of physical organic

chemistry with organic mechanisms.

The choice of this particular aspect came naturally because of the scarcity of books

on mechanistic inorganic chemistry, which has experienced an explosive growth in

recent years and has permeated other rapidly advancing areas such as bioinorganic,

organometallic, catalytic, and environmental chemistry. Some of the most complex

reactions and processes that are currently at the forefront of scientific endeavor rely

heavily on physical inorganic chemistry in search of new directions and solutions to

difficult problems. Solar energy harvesting and utilization, as well as catalytic

activation of small molecules as resources (carbon dioxide), fuels (hydrogen), or

reagents (oxygen), are just a few examples.

It is the goal of this book to present in one place the key features, methods, tools,

and techniques of physical inorganic chemistry, to provide examples where this

chemistry has produced a major contribution to multidisciplinary efforts, and to point

out the possibilities and opportunities for the future. Despite the enormous importance

and use of the more standard methods and techniques, those are not included here

because books and monographs have already been dedicated specifically to instru-

mental analysis and laboratory techniques. The 10 chapters in this book cover

inorganic and bioinorganic spectroscopy (Solomon and Bell), Mossbauer spectro-

scopy (Munck and Martinho), magnetochemical methods (Kogerler), cryoradiolysis

(Denisov), absolute chiral structures (Riehl and Kaizaki), flash photolysis and studies

of transients (Ferraudi), activation volumes (van Eldik and Hubbard), chemical

kinetics (Bakac), heavy atom isotope effects (Roth), and computational studies in

mechanistic transition metal chemistry (Harvey).

I am extending my gratitude to the authors of individual chapters who have given

generously of their time and wisdom to share their expertise with the reader. I am

grateful to my editor, Anita Lekhwani, for her professionalism, personal touch, and

ix

expert guidance through the entire publishing process. Finally, I thank my family,

friends, and coworkers who supported and helped me, and continued to have faith in

me throughout this long project.

ANDREJA BAKAC

x PREFACE

CONTRIBUTORS

ANDREJA BAKAC, The Ames Laboratory and Chemistry Department, Iowa State

University, Ames, IA, USA

CALEB B. BELL III, Department of Chemistry, Stanford University, Stanford, CA,

USA

ILIA G. DENISOV, Department of Biochemistry, University of Illinois at Urbana-

Champagne, Urbana, IL, USA

GUILLERMO FERRAUDI, Radiation Laboratory, University of Notre Dame, Notre

Dame, IN, USA

JEREMY N. HARVEY, Centre for Computational Chemistry, School of Chemistry,

University of Bristol, Bristol, UK

COLIN D. HUBBARD, Tolethorpe Close, Oakham, Rutland, UK

SUMIO KAIZAKI, Department of Chemistry, Center for Advanced Science and

Innovation, Graduate School of Science, Osaka University, Osaka, Japan

PAUL KOGERLER, Institut fur Anorganische Chemie, RWTH Aachen, Aachen,

Germany

MARLENE MARTINHO, Department of Chemistry, Carnegie Mellon University,

Pittsburgh, PA, USA

ECKARD MUNCK, Department of Chemistry, Carnegie Mellon University,

Pittsburgh, PA, USA

JAMES P. RIEHL, Department of Chemistry, University of Minnesota Duluth,

Duluth, MN, USA

JUSTINE P. ROTH, Department of Chemistry, Johns Hopkins University, Baltimore,

MD, USA

EDWARD I. SOLOMON, Department of Chemistry, Stanford University, Stanford, CA,

USA

RUDI VAN ELDIK, Institut fur Anorganische Chemie, Universitat Erlangen-

Nurnberg, Erlangen, Germany

xi