Charge Transfer Photochemistryof Coordination Compound s

Otto Horväth l and Kenneth L. Stevenson2

Introduction

xvi i

Part 1

1 Photochemical Laws

3

1 .1 Light and Energy

31 .2 Light Absorption

41 .3 Quantum Yields

61 .4 Types of Photochemical Experiments

71 .5 Light Sources

8References

9

2 Photochemistry and Photophysics

1 0

2.1 Quantum Mechanical Principles of Absorption

1 02.2 Energy Dissipation Pathways

1 42 .3 Photophysical Pathways: Luminescence and Nonradiative Decay

1 62.4 Photochemical Pathways

1 9References

20

3 Spectra and Photochemistry of Coordination

21.

Compounds

3 .1 Overview

2 13 .2 Ligand-to-Metal (LMCT) and Metal-to-Ligand (MLCT) Charge-

22Transfer Bands

3 .3 Charge-Transfer-to-Solvent (CTTS) Bands

2 53 .4 Other Charge Transfer Transitions

29References

30

Part 2

4 Copper, Silver, and Gold

3 5

4.1 Copper

3 54.1 .1 Copper(I) Complexes

3 54.1 .2 Copper(II) Complexes

4 94 .1 .3 Copper(III)

604.2 Silver

6 24.3 Gold

64References

66

5 Magnesium, Zinc, Cadmium, and Mercury

7 1

5 .1 Magnesium, Zinc, and Cadmium

7 15 .1 .1 Magnesium

7 15 .1.2 Zinc

735 .1 .3 Cadmium

745.2 Mercury

765 .2.1 Mercury(I)

765 .2.2 Mercury(II)

765 .2.3 Miscellaneous

79References

79

6 Aluminum, Gallium, Indium, Thallium, Yttrium,

83Lanthanides, and Actinides

6 .1 Aluminum, Gallium, and Indium

836.2 Thallium

846.3 Yttrium, Lanthanides, and Actinides

866 .3.1 Cerium

866 .3.2 Europium

8 96 .3.3 Uranium

946.3 .4 Uranyl Compounds

9 76 .3 .5 Other Lanthanides and Actinides

10 5References

107

7 Silicon, Germanium, Tin, Lead, and Titanium

11 3

7.1 Silicon and Germanium

11 37 .1 .1 Silicon

11 37 .1 .2 Germanium

11 37.2 Tin

11 57 .2 .1 Tin(II)

11 57 .2 .2 Tin(IV)

1167.3 Lead

11 97 .4 Titanium

120References

124

8 Antimony, Bismuth, Vanadium, Niobium, and

127

Tantalum

8 .1 Antimony

1278 .1 .1 Antimony(III)

1278 .1 .2 Antimony(V)

1298 .2 Bismuth

1298 .3 Vanadium

1308 .3 .1 Vanadium(II)

13 08 .3 .2 Vanadium(IV)

13 18 .3 .3 Vanadium(IV)

13 38 .3 .4 Vanadium(V)

13 48 .4 Niobium

13 98 .5 Tantalum

14 0References

14 1

9 Tellurium, Chromium, Molybdenum, and Tungsten

14 3

9.1 Tellurium

14 39.2 Chromium

14 59 .2.1 Chromium(H)

14 59 .2.2 Chromium(III)

14 69 .2.3 Chromium(VI) Compounds

15 29 .3 Molybdenum and Tungsten

15 69 .3 .1 Di- and Polynuclear Mo(II) and W(II) Complexes

15 69 .3 .2 Cyano and Thiocyanato Complexes

16 19 .3 .3 Other Molybdenum(V) Complexes

16 89 .3 .4 Molybdenum(VI) and Tungsten(VI) Complexes

17 3References

18 1

10 Manganese, Technetium, and Rhenium

18 7

10 .1 Manganese

18 710.1 .1 Complexes with Inorganic Ligands

18 710.1 .2 Acetylacetonato Complexes

190

10 .1 .3 Complexes of Macrocyclic and Chelate Ligands With N

19 2and 0 Coordination

10 .2 Technetium

19 6

10 .3 Rhenium

19 7

10 .3 .1 Halo and Oxohalo Complexes

19 7

10 .3 .2 Other Rhenium Complexes

20010 .3 .3 Organometallic Rhenium Complexes

202References

204

11 Iron, Ruthenium, and Osmium

207

11 .1 Iron

20711 .1 .1 Iron(II)

20811 .1 .2 Iron(In)

21 8

11 .2 Ruthenium and Osmium

230

11 .2 .1 Ruthenium(H) and Osmium(II)

230

11 .2 .2 Ruthenium(III) and Osmium(III)

247

11 .2 .3 Miscellany

249References

250

12 Cobalt, Rhodium, and Iridium

267

12 .1 Cobalt

26712 .1 .1 Cobalt(I)

26712 .1 .2 Cobalt(II)

26812 .1 .3 Cobalt(III)

27 112 .2 Rhodium and Iridium

29612.2 .1 Chloro Complexes

29812.2 .2 Diimine, Am(m)ine, and Cyano Complexes

29912.2 .3 Macrocyclic Complexes

30 112.2 .4 Bi- and Tetranuclear Complexes

30212.2 .5 Miscellany

304

References

304

13 Nickel, Palladium, and Platinum

312

13 .1 Nickel and Palladium

31213 .1 .1 Dithiolato Complexes

31313 .1 .2 Macrocyclic Complexes

31413 .1 .3 Mixed-Ligand a-Diimine, and Azido Complexes

31613 .1 .4 Oxalato Complexes

319

13 .1 .5 Miscellany

321

13 .2 Platinum

32 313 .2 .1 Platinum(I)

32 313 .2 .2 Platinum(III)

33 513 .2 .3 Platinum(IV)

339

References

348

Appendices

353

Appendix 1: Abbreviations

35 3Appendix 2: Additional References

35 8

Material Index

36 3

Subject Index

373