Contents XI 7.33.3.2 Functionalization by Oxidative Insertion 273 7.3.33.3 Functionalization by O-Atom Insertion 276 7.4 Conclusions and Perspective for Methane Functionalization 282 References 283 Water Activation:Catalytic Hydrolysis 287 Lisa M Rerreau 8.1 Introduction 287 8.1.1 Water Activation 287 8.1.2 Catalytic Hydrolysis 287 8.2 Water Activation:Coordination Sphere Effects on M-OH2 Acidity mary C tion Environment 288 ng.293 8.2.3 amolecular H-Bonding and Mononuclear Zn-OH Stabilization 29 8.2.4 Structural Effects Derived from M-OH2 Acting as an Intramolecular H-Bond Donor to a Bound Phosphate Ester 298 8.2.5 Ligand Effects on the pK of a Metal-bound Water in Co(III) and Fe(IIl)Complexes 299 8.2.6 Acidity and Water Exchange Properties of Organometallic Aqua 10mg300 8.3 Secondary H-Bonding Effects on Substrate Coordination.Activation and Catalytic hydrolysis Involving phosphate esters 302 8.31 H-Bonding and Phosphate Ester Coordination to a Metal Center 01 8.3.2 H-Bondin and Stochiometric and Catalytic Phosphate Ester Hydrolysis 204 8.4 mary an Future Directions 312 rences 314 9 Carbon Monoxide as a Chemical Feedstock Carbonylation Catalysis 319 Piet W.N.M.van Leeuwen and Zoraida Freixa Introduction 319 9.1.1 Heterogeneous processes 319 9.12 Homogeneous Catalysts 321 Rhodium-catalyzed Hydroformylation 322 9.2.1 Introduction 322 9.2.2 Co as the ligand 323 9.2.3 Phosphites as Ligands 324 9.2.4 osphines 328 9.2.4.1 hin 328 14 kenes7.3.3.3.2 Functionalization by Oxidative Insertion 273 7.3.3.3.3 Functionalization by O-Atom Insertion 276 7.4 Conclusions and Perspective for Methane Functionalization 282 References 283 8 Water Activation: Catalytic Hydrolysis 287 Lisa M. Berreau 8.1 Introduction 287 8.1.1 Water Activation 287 8.1.2 Catalytic Hydrolysis 287 8.2 Water Activation: Coordination Sphere Effects on M-OH2 Acidity and Structure 288 8.2.1 Primary Coordination Environment 288 8.2.2 Secondary H-Bonding 293 8.2.3 Intramolecular H-Bonding and Mononuclear Zn-OH Stabilization 297 8.2.4 Structural Effects Derived from M-OH2 Acting as an Intramolecular H-Bond Donor to a Bound Phosphate Ester 298 8.2.5 Ligand Effects on the pKa of a Metal-bound Water in Co(III) and Fe(III) Complexes 299 8.2.6 Acidity and Water Exchange Properties of Organometallic Aqua Ions 300 8.3 Secondary H-Bonding Effects on Substrate Coordination, Activation and Catalytic Hydrolysis Involving Phosphate Esters 302 8.3.1 H-Bonding and Phosphate Ester Coordination to a Metal Center 302 8.3.2 H-Bonding and Stochiometric and Catalytic Phosphate Ester Hydrolysis 304 8.4 Summary and Future Directions 312 References 314 9 Carbon Monoxide as a Chemical Feedstock: Carbonylation Catalysis 319 Piet W.N.M. van Leeuwen and Zoraida Freixa 9.1 Introduction 319 9.1.1 Heterogeneous Processes 319 9.1.2 Homogeneous Catalysts 321 9.2 Rhodium-catalyzed Hydroformylation 322 9.2.1 Introduction 322 9.2.2 CO as the Ligand 323 9.2.3 Phosphites as Ligands 324 9.2.4 Arylphosphines as Ligands 328 9.2.4.1 Monophosphines 328 9.2.4.2 Diphosphines 329 9.2.4.2.1 1-Alkenes 333 Contents XI