Advances in Inorganic Chemistry

Advances in Inorganic Chemistry Volume 58 focuses on homogeneous biomimetic oxidation catalysis. Contributions by leading experts in the field cover important advances in inorganic and bioinorganic chemistry. Contributions include diversity-based approaches to selective biomimetic oxidation catalysis; the selective conversion of hydrocarbons with H2O2 using biomimetic non-heme iron and manganese oxidation catalysis; DNA oxidation by copper and manganese complexes; influences of the ligand in copper-dioxygen complex-formation and substrate oxidations; biomimetic oxidations by dinuclear and trinuclear copper complexes. In the final contribution the authors focus on green oxidation of alcohols using biomimetic copper complexes and enzymes as catalysts. Volume 58 provides another welcomed addition to the widely acclaimed series, Advances in Inorganic Chemistry. * Includes new information on the important advances in inorganic and bioinorganic chemistry * Each chapter is fully referenced * Contains comprehensive reviews written by leading experts in the field

PREFACE

vii

Diversity-Based Approaches to Selective Biomimetic Oxidation Catalysis

ALBRECHT BERKESSEL

I. Introduction

1

(6)

A. Combinatorial methods in catalysis research

4

(1)

B. Library generation

4

(1)

C. Screening methodology

5

(1)

D. Opportunities for diversity-based methods in biomimetic oxidation catalysis: enzyme models and enzymes

6

(1)

II. Biomimetic oxidation catalysis based on metal complexes

7

(10)

A. Asymmetric epoxidation of olefins

7

(3)

B. Asymmetric sulfoxidation of thioethers

10

(3)

C. Baeyer-Villiger oxidation of ketones

13

(1)

D. Air oxidation of alcohols

14

(3)

III. Biomimetic oxidation catalysis based on purely organic catalysts

17

(5)

A. Iminium-ion catalyzed asymmetric epoxidation of olefins

17

(2)

B. Peptide and peptoid catalysts for the asymmetric epoxidation of enones

19

(3)

IV. Directed evolution of enzymes for oxidation catalysis

22

(4)

Epilogue

26

(1)

Acknowledgments

26

(1)

References

26

(3)

Selective Conversion of Hydrocarbons with H202 Using Biomimetic Non-heme Iron and Manganese Oxidation Catalysts

STEFANIA TANASE and ELISABETH BOUWMAN

I. General introduction

29

(2)

II. Biological enzymes and catalytic oxidation

31

(6)

A. Introduction

31

(1)

B. Non-home iron enzymes

31

(3)

C. Manganese redox enzymes

34

(3)

D. Ligand design for biomimetic non-heme iron and manganese complexes

37

(1)

III. Biomimetic iron catalysts

37

(18)

A. Alkane hydroxylation

37

(12)

B. cis-Dihydroxylation vs. olefin epoxidation

49

(4)

C. Aromatic hydroxylation

53

(1)

D. Role of additives

54

(1)

IV. Biomimetic manganese catalysts

55

(13)

A. Alkane oxidation

55

(1)

B. Olefin epoxidations

56

(10)

C. cis-Dihydroxylation

66

(2)

V. Concluding remarks

68

(1)

Acknowledgments

69

(1)

References

70

DNA Oxidation by Copper and Manganese Complexes

MARGUERITE PITIÉ, CHRISTOPHE BOLDRON and GENEVIÈVE PRATVIEL

I. Introduction

77

(1)

II. Oxidative DNA cleavage by copper complexes

78

(21)

A. Copper phenanthroline

78

(11)

B. Copper Clip-Phen

89

(4)

C. Generalities upon copper complexes able to cleave DNA

93

(6)

III. Oxidative DNA damage by manganese complexes

99

(21)

A. High-valent manganese-oxo species

99

(4)

B. Manganese salen or related complexes

103

(1)

C. Manganese bleomycin

104

(1)

D. Manganese porphyrin

105

(15)

IV. Conclusion

120

(3)

Abbreviations

Acknowledgments

123

(1)

References

123

(8)

Ligand Influences in Copper-Dioxygen Complex-Formation and Substrate Oxidations

LANYING Q. HATCHER and KENNETH D. KARLIN

I. Introduction

131

(9)

A. Biological inspiration

132

(3)

B. Synthetic Cun:O2 structural/spectroscopic types

135

(5)

II. Tetradentate ligand influences

140

(7)

A. Chelate ring size effects

142

(1)

B. Electronic effects in tetradentate ligand systems

143

(2)

C. Tetradentate vs. tridentate ligand influences in dioxygen reactivity

145

(1)

D. Unusual structures with tetradentate ligands

146

(1)

III. Tridentate ligand influences: Side-on peroxo vs. bis(μ-oxo) equilibrium

147

(15)

A. Environmental factors

148

(3)

B. Specific tridentate ligand influences on the peroxo/bis(μ-oxo) equilibrium

151

(8)

C. Tridentate ligand influences: Binucleating ligand constraints

159

(2)

D. Summary of ligand effects on copper-dioxygen reactivity

161

(1)

IV. Ligand effects on the exogenous substrate reactivity of Cu2O2 compounds

162

(16)

A. End-on vs. side-on peroxo reactivity – initial studies

162

(2)

B. Reactivity of side-on peroxo and bis(μ-oxo) complexes

164

(1)

C. Aromatic hydroxylation

165

(2)

D. Intermolecular oxidations

167

(2)

E. Mechanistic studies

169

(9)

V. Summary and outlook

178

(2)

References

180

(5)

Biomimetic Oxidations by Dinuclear and Trinuclear Copper Complexes

GIUSEPPE BATTAINI, ALESSANDRO GRANATA, ENRICO MONZANI, MICHELE GULLOTTI and LUIGI CASELLA

I. Copper proteins containing dinuclear and trinuclear metal clusters

185

(10)

A. Introduction

185

(2)

B. Dinuclear copper proteins and enzymes

187

(5)

C. Multicopper oxidases

192

(3)

II. Biomimetic oxidations by dinuclear complexes as tyrosinase and catechol oxidase models: General aspects

195

(4)

III. Phenolase activity

199

(13)

A. Intramolecular ligand oxidations

199

(5)

B. Reactions on exogenous phenolic substrates

204

(8)

IV. Catecholase activity

212

(10)

V. Oxidations by trinuclear complexes

222

(4)

VI. Conclusions

226

(1)

Acknowledgments

227

(1)

References

227

(8)

Green Oxidation of Alcohols using Biomimetic Cu Complexes and Cu Enzymes as Catalysts

ISABEL W.C.E ARENDS, PATRICK GAMEZ and ROGER A. SHELDON

I. Introduction

235

(2)

A. Galactose oxidase

237

(3)

B. Lactase

240

II. Enzymatic systems using Cu-oxidases

237

(7)

A. Bio-inspired catalysts using dioxygen as oxidant: [Copper(II)-Schiff base] catalyst)

246

(4)

B. [CuII(2,2' -thiobis(2,4 -di-tert-butylphenol))] catalyst

250

(6)

C. [Cu2II(2 -(Methylthio)- 4 -tert-butyl- 6 -[[bis [2 -(2 -pyridyDethyl] amino] - methyll-phenol)2](PF6)2 catalyst

256

(2)

D. [CuII(N,N-bis(2 -hydroxy- 3,5 -di-tert-butylbenzy1)-1,2 -ethylene diamine)] catalyst

258

(1)

E. CuICl(phen)—DBADH2

258

(5)

F. Copper-TEMPO catalytic systems

263

(11)

G. Cu-salen using dihydrogen peroxide as oxidant

274

III. Biomimetic systems for alcohol oxidation

244

(33)

IV. Future outlook

References

277

INDEX

CONTENTS OF PREVIOUS VOLUMES

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Advances in Inorganic Chemistry

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