Activation of Small Molecules: Organometallic and Bioinorganic Perspectives

The activation of small molecules, such as nitrogen, oxygen or hydrogen, has always been a major research topic in the field of bioinorganic chemistry. 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. Also the activation of molecular oxygen is still a challenge and would lead to atom–efficient and green oxidation processes.
This handbook provides highlights of recent research, with an emphasis on newly discovered fundamental chemistry involved in metal–mediated binding and activation of CO2, CO, NO, N2O, N2, H2, CH4, H2O, and O2. By bringing together concise, yet detailed reviews by experts in these wide–ranging fields, it offers cross–disciplinary insights in one convenient volume. Importantly, by organizing each chapter by small molecule, organometallic and bioinorganic perspectives are often discussed together, in comparative fashion, thus bridging the two disciplines and generating new, unifying concepts.
Taken together, the chapters illustrate the diversity of metal systems used in the laboratory and by nature to capture and use small molecules. Challenges for the future are sprinkled throughout, making this a valuable resource for students and researchers.

Spis treści:
Preface.
List of Contributors.
1 Carbon Dioxide Reduction and Uses as a Chemical Feedstock (Michele Aresta).
1.1 Introduction.
1.2 Properties of the CO2 Molecule.
1.3 CO2 Coordination to Metal Centers and Reactivity of Coordinated
CO2.
1.4 CO2 Conversion.
1.5 Conclusions.
References.
2 Nitrogen Monoxide and Nitrous Oxide Binding and Reduction ( Dong–Heon Lee, Biplab Mondal, and Kenneth D. Karlin).
2.1 Introduction.
2.2 NO.
2.3 N2O.
2.4 Summary and Conclusions.
References.
3 Bio–organometallic Approaches to Nitrogen Fixation Chemistry (Jonas C. Peters and Mark P. Mehn).
3.1 Introduction – The N2 Fixation Challenge.
3.2 Biological N2 Reduction.
3.3 Biomimetic Systems that Model Structure and Function.
3.4 Concluding Remarks.
References.
4 The Activation of Dihydrogen (Jesse W. Tye and Michael B. Hall).
4.1 Introduction.
4.2 Structure and Bonding of Metal–bound H–Atoms.
4.3 Intramolecular H–Atom Exchange.
4.4 Nonclassical H–Bonds.
4.5 Reactivity of Metal–bound H–Atoms.
4.6 Recent Advances in the Activation of Dihydrogen by Synthetic Complexes.
4.7 Enzymatically Catalyzed Dihydrogen Oxidation and Proton Reduction.
4.8 Conclusions.
Acknowledgments.
Abbreviations.
References.
5 Molecular Oxygen Binding and Activation: Oxidation Catalysis (Candace N. Cornell and Matthew S. Sigman).
5.1 Introduction.
5.2 Additive Coreductants.
5.3 Ligand–modified Catalysis.
5.4 Conclusions and Outlook.
References.
6 Dioxygen Binding and Activation: Reactive Intermediates (Andrew S. Borovik, Paul J. Zinn and Matthew K. Zart).
6.1 Introduction.
6.2 Dioxygen Binders.
6.3 Reactive Intermediates: Iron and Copper Species.
6.4 Cobalt–Dioxygen Complexes.
6.5 Manganese–Dioxygen Complexes.
6.6 Nickel–Dioxygen Complexes and Their Reactive Intermediates.
6.7 Summary.
Acknowledgments.
References.
7 Methane Functionalization (Brian Conley, William J. Tenn, III, Kenneth J.H. Young, Somesh Ganesh, Steve Meier, Jonas Oxgaard, Jason Gonzales, William A. Goddard, III, and Roy A. Periana).
7.1 Methane as a Replacement for Petroleum.
7.2 Low Temperature is Key to Economical Methane Functionalization.
7.3 CH Activation as a Pathway to Economical Methane Functionalization via CH Hydroxylation.
7.4 Conclusions and Perspective for Methane Functionalization.
References.
8 Water Activation: Catalytic Hydrolysis (Lisa M. Berreau).
8.1 Introduction.
8.2 Water Activation: Coordination Sphere Effects on M–OH2 Acidity and Structure.
8.3 Secondary H–Bonding Effects on Substrate Coordination, Activation and Catalytic Hydrolysis Involving Phosphate Esters.
8.4 Summary and Future Directions.
References.
9 Carbon Monoxide as a Chemical Feedstock: Carbonylation Catalysis (Piet W.N.M. van Leeuwen and Zoraida Freixa).
9.1 Introduction.
9.2 Rhodium–catalyzed Hydroformylation.
9.3 Methanol Carbonylation.
9.4 Concluding Remarks.
References.
Subject Index.

Nota biograficzna:
William B. Tolman is a distinguished McKnight University and L.I. Smith Professor at the Department of Chemistry and Center for Metals in Biocatalysis at the University of Minnesota. His many awards include an Alexander von Humboldt Foundation Research Award, a Camille & Henry Dreyfus Teacher–Scholar Award, an Alfred P. Sloan Foundation Research Fellowship, and a National Young Investigator Award from the U.S. National Science Foundation. He is a Fellow of the Royal Society of Chemistry and a member of the American Chemical Society, the Society for Biological Inorganic Chemistry, and the American Association for the Advancement of Science. Professor Tolman′s research interests focus on synthetic modeling of copper and iron protein active sites and the development of catalytic processes for the preparation of biodegradable polymers from renewable resources.

Okładka tylna:
The activation of small molecules, such as nitrogen, oxygen or hydrogen, has always been a major research topic in the field of bioi norganic chemistry. 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. Also the activation of molecular oxygen is still a challenge and would lead to atom–efficient and green oxidation processes.
This handbook provides highlights of recent research, with an emphasis on newly discovered fundamental chemistry involved in metal–mediated binding and activation of CO2, CO, NO, N2O, N2, H2, CH4, H2O, and O2. By bringing together concise, yet detailed reviews by experts in these wide–ranging fields, it offers cross–disciplinary insights in one convenient volume. Importantly, by organizing each chapter by small molecule, organometallic and bioinorganic perspectives are often discussed together, in comparative fashion, thus bridging the two disciplines and generating new, unifying concepts.
Taken together, the chapters illustrate the diversity of metal systems used in the laboratory and by nature to capture and use small molecules. Challenges for the future are sprinkled throughout, making this a valuable resource for students and researchers.