www.jamshimi.ir www.jamshimi.ir www.jamshimi.ir PHYSICAL INORGANIC CHEMISTRY www.jamshimi.ir www.jamshimi.ir PHYSICAL INORGANIC CHEMISTRY Principles, Methods, and Models Edited by Andreja Bakac www.jamshimi.ir Copyright Ó 2010 by John Wiley & Sons, Inc. All rights reserved. Published by John Wiley & Sons, Inc., Hoboken, New Jersey Published simultaneously in Canada No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4470, or on the web at www.copyright.com. 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QD475.P49 2010 547’.13–dc22 2009051003 Printed in the United States of America 10987654321 www.jamshimi.ir To Jojika www.jamshimi.ir CONTENTSwww.jamshimi.ir Preface ix Contributors xi 1 Inorganic and Bioinorganic Spectroscopy 1 Edward I. Solomon and Caleb B. Bell III 2 57Fe Mossbauer€ Spectroscopy in Chemistry and Biology 39 Marlene Martinho and Eckard Munck€ 3 Magnetochemical Methods and Models in Inorganic Chemistry 69 Paul Kogerler€ 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 Heavy Atom Isotope Effects as Probes of Small Molecule Activation 425 Justine P. Roth 10 ComputationalStudies ofReactivity inTransitionMetalChemistry 459 Jeremy N. Harvey Index 501 vii www.jamshimi.ir PREFACEwww.jamshimi.ir 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), Mo¨ssbauer spectro- scopy (Mu¨nck and Martinho), magnetochemical methods (Ko¨gerler), 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 x PREFACE 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 throughoutwww.jamshimi.ir this long project. ANDREJA BAKAC CONTRIBUTORSwww.jamshimi.ir 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 KO¨ GERLER, Institut fu¨r Anorganische Chemie, RWTH Aachen, Aachen, Germany MARLE` NE MARTINHO, Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA, USA ECKARD MU¨ NCK, 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 fu¨r Anorganische Chemie, Universita¨t Erlangen- Nu¨rnberg, Erlangen, Germany xi www.jamshimi.ir 1 Inorganicwww.jamshimi.ir and Bioinorganic Spectroscopy EDWARD I. SOLOMON and CALEB B. BELL III 1.1 INTRODUCTION Spectroscopic methods have played a critical and symbiotic role in the development of our understanding of the electronic structure, physical properties, and reactivity of inorganic compounds and active sites in biological catalysis.1,2 Ligand field theory3 developed with our understanding of the photophysical and magnetic properties of transition metal complexes. Ligand–metal (L–M) bonding descriptions evolved through the connection of p-donor interactions with ligand to metal charge transfer (LMCT) transitions and p-backbonding with metal to ligand charge transfer (MLCT) transitions.4 X-ray absorption (XAS) spectroscopy initially focused on the use of extended X-ray absorption fine structure5 (EXAFS) to determine the geometric structure of a metal site in solution, but evolved in the analyses of pre-edges and edges to probe the electronic structure and thus covalency of ligand–metal bonds.6 In bioinorganic chemistry, spectroscopy probes the geometric and electronic structure of a metallobiomolecule active site allowing the correlation of structure with function (Figure 1.1).7 Spectroscopies are also used to experimentally probe transient species along a reaction coordinate, where often the sample has been rapidly freeze quenched to trap intermediates. An important theme in bioinorganic chemistry is that active sites often exhibit unique spectroscopic features, compared to small model complexes with the same metal ion.8 These unusual spectroscopic features