Contents Preface XIII List of Contributors XV Carbon Dioxide Reduction and Uses as a Chemical Feedstock 1 Michele Aresta 1.1 Introduction 1 1.2 Properties of the CO2 Molecule 3 1.2.1 Molecular Geometry 3 122 Spectroscopic Properties 3 1221 Vibrational 3 1.2.2.2 UV-Vis 4 1.223 BC.Nuclear magnetic Reson 123 Data and Re. etics Rel 5 13 action of Cowith Metal Atoms at ow Temperature:Stabilit of the 13.3 Reactivity of CO2 Coordinated to Transition Metal Systems 8 1.4 CO,Conversion 9 1.4.1 Carboxylation Reactions 10 1.4.1.1 C-C Bond Formation 10 1.41.1.1 Natural Processes 11 1.4.1.1.2 Artificial Processes 12 1412 N-C Bond Formation 16 1413 O-C Bond Formation 18 1.4131 Cyclic Carbonates 18 14132 ates 1414 Use of Urea 26 1.4.15 as ap cation ns 1.4.2 Red action ReactionsPreface XIII List of Contributors XV 1 Carbon Dioxide Reduction and Uses as a Chemical Feedstock 1 Michele Aresta 1.1 Introduction 1 1.2 Properties of the CO2 Molecule 3 1.2.1 Molecular Geometry 3 1.2.2 Spectroscopic Properties 3 1.2.2.1 Vibrational 3 1.2.2.2 UV-Vis 4 1.2.2.3 13C-Nuclear Magnetic Resonance (NMR) 4 1.2.3 Energy Data and Reaction Kinetics Relevant to CO2 Conversion 5 1.3 CO2 Coordination to Metal Centers and Reactivity of Coordinated CO2 6 1.3.1 Modes of Coordination 6 1.3.2 Interaction of CO2 with Metal Atoms at Low Temperature: Stability of the Adducts 8 1.3.3 Reactivity of CO2 Coordinated to Transition Metal Systems 8 1.4 CO2 Conversion 9 1.4.1 Carboxylation Reactions 10 1.4.1.1 C–C Bond Formation 10 1.4.1.1.1 Natural Processes 11 1.4.1.1.2 Artificial Processes 12 1.4.1.2 N–C Bond Formation 16 1.4.1.3 O–C Bond Formation 18 1.4.1.3.1 Cyclic Carbonates 18 1.4.1.3.2 Linear Carbonates 22 1.4.1.4 Use of Urea as an Active-CO2 Form 26 1.4.1.5 Transesterification Reactions 27 1.4.2 Reduction Reactions 28 V Activation of Small Molecules. Edited by William B. Tolman Copyright © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 3-527-31312-5 Contents