Preface urse .simple small mole cules like H2. onewho has taken a basic chemistry nd o. e ubiquitous reser oirs cal 8 These en sourc vay system and as synth construc re complex m they may serve as signaling agents in biologic syste gger complex pre tein expressic on processes.Such small mole ecu sare generally quite therm odynamically stable and their successful utilization depends on sur mounting often quite significant kinetic barriers.It has long been recognized that metal ions play an important role in providing low-barrier reaction path- ways through binding and activation events.Much fundamental chemistry re. search has therefore been aimed at addressing questions such as: How do metal ions coordinate to and modulate the reactivity of small,often rather inert molecules? What is the basis for the selectivity of natural and synthetic me- tal-containing systems for specific small-molecule substrates? one use kr owledge of metal/small-molecule che istn for he dev catalytic processes useful in the lab These and other related ve synthet is to provide recent research,with emphasis on newly discovered fundamental chemistry in- volved in metal-mediated binding and activation of CO2,CO,NO,N2O,N2.H2, CH4.H2O and O2.This work has led to a deep understanding that has signifi cantly impacted the fields of bioinorganic,organometallic and catalytic chemis- try.By bringing together concise,yet detailed reviews by experts in these wide. ranging fields into a single volume,cross-disciplinary insights are provided in a valuable resource for students and researchers.Importantly.by organizing each chapter by small molecule,organometallic and bioinorganic perspectives are dis. cussed together,in co ompara ve fashion,thus bridging the two atin ndu pr oof the reenhous sized in Chapter 1 by M. e gas CO. comparisons a rawn logical pro
Familiar to anyone who has taken a basic chemistry course, simple small molecules like H2, N2 and O2 are ubiquitous reservoirs of chemical energy. These energy sources may be used in many ways, such as for fueling biological systems and as synthons for the construction of more complex molecules. Moreover, they may serve as signaling agents in biological systems to trigger complex protein expression and regulation processes. Such small molecules are generally quite thermodynamically stable and their successful utilization depends on surmounting often quite significant kinetic barriers. It has long been recognized that metal ions play an important role in providing low-barrier reaction pathways through binding and activation events. Much fundamental chemistry research has therefore been aimed at addressing questions such as: How do metal ions coordinate to and modulate the reactivity of small, often rather inert molecules? What is the basis for the selectivity of natural and synthetic metal-containing systems for specific small-molecule substrates? Can one use knowledge of metal/small-molecule chemistry for the development of new catalytic processes useful in the laboratory and/or in industry? These and other related questions have been addressed in the past 10–15 years through the application of creative synthetic strategies and advanced experimental and theoretical techniques. The aim of this book is to provide highlights of recent research, with emphasis on newly discovered fundamental chemistry involved in metal-mediated binding and activation of CO2, CO, NO, N2O, N2, H2, CH4, H2O and O2. This work has led to a deep understanding that has significantly impacted the fields of bioinorganic, organometallic and catalytic chemistry. By bringing together concise, yet detailed reviews by experts in these wideranging fields into a single volume, cross-disciplinary insights are provided in a valuable resource for students and researchers. Importantly, by organizing each chapter by small molecule, organometallic and bioinorganic perspectives are discussed together, in comparative fashion, thus bridging the two disciplines and generating new, unifying concepts. Industrial processes for the utilization of the greenhouse gas CO2 are emphasized in Chapter 1 by M. Aresta, with comparisons also drawn to biological proXIII Activation of Small Molecules. Edited by William B. Tolman Copyright © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 3-527-31312-5 Preface
cesses.Chapter 2 by D.H.Lee,B.Mondal and K.D.Karlin focuses on NO and N2O reduction using examples drawn broadly from coordination and organome. tallic chemistry,as well as biological systems.Mechanisms of reduction of N and synthetic model systems are discussed by I.Peter and M Mehn 3 while in ch apter .W.Tye and d M.Hall id H2 bindi an met an loprotei topic o on is pres an by C.N M Sigman an A P.. and M. re spectively Comp ntary vews emistry are provi d in the chapters through discussion of mechanisms oxidation catalysis and reactive in- termediate characterization.The enormously important problem of methane functionalization is tackled in Chapter 7 by R.Periana.The role of metal-aquo complexes in bioinorganic catalysis is emphasized in Chapter 8 by L.Berreau, before turning back to industrial applications in the discussion of CO chemistry by P.W.N.M van Leeuwen and Z.Freixa in Chapter 9.Taken together,these chapters illustrate the diversity of,and provide detailed mechanistic insights into,metal systems that are used in the laboratory and by nature to capture and use small molecules.Challenges for the future are laced throughout,and it is hoped that the reader will be stimulated to address them in future research. Department of Chemistry and Center for Metals Minneapolis,MN June 2006
cesses. Chapter 2 by D.H. Lee, B. Mondal and K. D. Karlin focuses on NO and N2O reduction using examples drawn broadly from coordination and organometallic chemistry, as well as biological systems. Mechanisms of reduction of N2 by nitrogenase and synthetic model systems are discussed by J. Peters and M. Mehn in Chapter 3, while in Chapter 4, J.W. Tye and M. Hall provide a tutorial on H2 binding and reduction by metal complexes and metalloproteins. The broad topic of O2 coordination and activation is presented in Chapters 5 and 6 by C.N. Cornall and M. Sigman and A. Borovik, P. J. Zinn and M.K. Zart, respectively. Complementary views of metal–O2 chemistry are provided in these chapters through discussion of mechanisms, oxidation catalysis and reactive intermediate characterization. The enormously important problem of methane functionalization is tackled in Chapter 7 by R. Periana. The role of metal–aquo complexes in bioinorganic catalysis is emphasized in Chapter 8 by L. Berreau, before turning back to industrial applications in the discussion of CO chemistry by P. W. N.M van Leeuwen and Z. Freixa in Chapter 9. Taken together, these chapters illustrate the diversity of, and provide detailed mechanistic insights into, metal systems that are used in the laboratory and by nature to capture and use small molecules. Challenges for the future are laced throughout, and it is hoped that the reader will be stimulated to address them in future research. W.B. Tolman Department of Chemistry and Center for Metals in Biocatalysis University of Minnesota Minneapolis, MN 55455 USA June 2006 XIV Preface
w List of Contributors Michele Aresta Zoraida Freixa Department of Chemistry Institut Catala d'Investigacio Quimica University of Bari 43007 Tarragona 70126 Bari Spain Italy Kenneth D.Karlin Andrew S.Borovik nt of Ch emis ns ur 10 of Che Univers USA Somesh Ganesh Donald P.and Katherine B.Loker Lisa M.Berreau Hydrocarbon Research Institute Department of Chemistry Department of Chemistry and Biochemistry University of Southern California Utah State University Los Angeles.CA 90089 Logan,UT84322-0300 USA USA William A.Goddard.Il Materials and Pro ess Simulation rbon Res earch Institut Institute Division Chemistry and Chemical versit USA ngeles,CA 90089 of Technology Pasadena,CA9112 USA Candace N.Cornell University of Utah Department of Chemistry Salt Lake City,Utah 84112-0850 USA
XV Activation of Small Molecules. Edited by William B. Tolman Copyright © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 3-527-31312-5 List of Contributors Michele Aresta Department of Chemistry University of Bari 70126 Bari Italy Andrew S. Borovik Department of Chemistry 1102 Natural Sciences II University of California Irvine, CA 92697-2025 USA Lisa M. Berreau Department of Chemistry and Biochemistry Utah State University Logan, UT 84322-0300 USA Brian Conley Donald P. and Katherine B. Loker Hydrocarbon Research Institute Department of Chemistry University of Southern California Los Angeles, CA 90089 USA Candace N. Cornell University of Utah Department of Chemistry Salt Lake City, Utah 84112-0850 USA Zoraida Freixa Institut Catalá d‘Investigació Química 43007 Tarragona Spain Kenneth D. Karlin Department of Chemistry Johns Hopkins University Baltimore, MD 21218-2685 USA Somesh Ganesh Donald P. and Katherine B. Loker Hydrocarbon Research Institute Department of Chemistry University of Southern California Los Angeles, CA 90089 USA William A. Goddard, III Materials and Process Simulation Center Beckman Institute Division of Chemistry and Chemical Engineering California Institute of Technology Pasadena, CA 91125 USA
XVI List of Contributor lason Gonzales lonas Oxgaard Materials and Process Simulation Materials and Process Simulation Center Center Beckman Institute of Chemistry and Chemical ia of Technology ornia stitute of Technology lena,CA 91125 lena,CA 91125 USA USA Michael B.Hall Roy A.Periana Department of Chemistry Donald P.and Katherine B.Loker Texas A M University Hydrocarbon Research Institute College Station,TX 77842-3255 Department of Chemistry USA University of Southern California Los Angeles.CA 90089 Dong-Heon Lee USA rtment of Chemistry lonas C.Peters Laboratories of Chemical Syn thesis Depar of Ch cal Engm try and eri California In of Technology Chemical Synthesis Department of Chemistry and USA Chemical Engineering California Institute of Technology Matthew Sigman Pasadena,CA91125 University of Utah USA Department of Chemistry Salt Lake City.Utah 84112-0850 Steve Meier USA Donald P.and Katherine B.Loker Hydrocarbon Research Institute William I.Tenn.Ill rtment of Che Donald P.and Katherine B.Loker Rese: arch Institute ngele ,CA90089 USA Angeles,CA 90089 Biplab Mondal USA Department of Chemistry IIT-Guwahati North Guwahat Assam 781039 India
XVI List of Contributors Jason Gonzales Materials and Process Simulation Center Beckman Institute Division of Chemistry and Chemical Engineering California Institute of Technology Pasadena, CA 91125 USA Michael B. Hall Department of Chemistry Texas A & M University College Station, TX 77842-3255 USA Dong-Heon Lee Department of Chemistry Chonbuk National University Jeonju 561-756 Korea Mark P. Mehn Arnold and Mabel Beckman Laboratories of Chemical Synthesis Department of Chemistry and Chemical Engineering California Institute of Technology Pasadena, CA 91125 USA Steve Meier Donald P. and Katherine B. Loker Hydrocarbon Research Institute Department of Chemistry University of Southern California Los Angeles, CA 90089 USA Biplab Mondal Department of Chemistry IIT – Guwahati North Guwahati Assam 781039 India Jonas Oxgaard Materials and Process Simulation Center Beckman Institute Division of Chemistry and Chemical Engineering California Institute of Technology Pasadena, CA 91125 USA Roy A. Periana Donald P. and Katherine B. Loker Hydrocarbon Research Institute Department of Chemistry University of Southern California Los Angeles, CA 90089 USA Jonas C. Peters Arnold and Mabel Beckman Laboratories of Chemical Synthesis Department of Chemistry and Chemical Engineering California Institute of Technology Pasadena, CA 91125 USA Matthew Sigman University of Utah Department of Chemistry Salt Lake City, Utah 84112-0850 USA William J. Tenn, III Donald P. and Katherine B. Loker Hydrocarbon Research Institute Department of Chemistry University of Southern California Los Angeles, CA 90089 USA
List of ContributorsXVI Jesse W.Tye Matthew K.Zart Department of Chemistry Department of Chemistry Texas A M University University of Kansas College Station.TX 77842-3255 Lawrence.KD 66047 USA USA Piet W.N.M.van Leeuwen Paul I.Zinn Van't Hoff Institute for Molecular Department of Chemistry Sciences University of Kansas Faculty of sciences Lawrence,KD66047 Univ USA Amste Kenneth J.H.Young Donald P.and Katherine B.Loke Hydrocarbon Research Institute Department of Chemistry University of Southern California Los Angeles.CA 90089 USA
List of Contributors XVII Jesse W. Tye Department of Chemistry Texas A & M University College Station, TX 77842-3255 USA Piet W. N. M. van Leeuwen Van‘t Hoff Institute for Molecular Sciences Faculty of Sciences Universiteit van Amsterdam 1018 Amsterdam The Netherlands Kenneth J. H. Young Donald P. and Katherine B. Loker Hydrocarbon Research Institute Department of Chemistry University of Southern California Los Angeles, CA 90089 USA Matthew K. Zart Department of Chemistry University of Kansas Lawrence, KD 66047 USA Paul J. Zinn Department of Chemistry University of Kansas Lawrence, KD 66047 USA