Progress in Inorganic Chemistry, Volume 58 E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Veröffentlichungsjahr: 2014

Beschreibung

This series provides inorganic chemists and materials scientists with a forum for critical, authoritative evaluations of advances in every area of the discipline. Volume 58 continues to report recent advances with a significant, up-to-date selection of contributions by internationally-recognized researchers.

The chapters of this volume are devoted to the following topics:

• Tris(dithiolene) Chemistry: A Golden Jubilee
• How to find an HNO needle in a (bio)-chemical Haystack
• Photoactive Metal Nitrosyl and Carbonyl Complexes Derived from Designed Auxiliary Ligands: An Emerging Class of Photochemotherapeutics
• Metal--Metal Bond-Containing Complexes as Catalysts for C--H Functionalization Iron Catalysis in Synthetic Chemistry
• Reactive Transition Metal Nitride Complexes

Suitable for inorganic chemists and materials scientists in academia, government, and industries including pharmaceutical, fine chemical, biotech, and agricultural. 

Leseprobe

CONTENTS

Cover

Advisory Board

Title Page

Copyright

Chapter 1: Tris(dithiolene) Chemistry: A Golden Jubilee

I. Introduction

II. Ligands

III. Complexes

IV. Structures

V. Theory

VI. Electrochemistry

VII. Magnetometry

VIII. Spectroscopy

IX. Summary

X. Conclusions

Acknowledgments

Abbreviations

References

Chapter 2: How to Find an HNO Needle in a (Bio)-Chemical Haystack

I. Introduction

II. Chemical and Biological Relevance of HNO

III. Azanone Detection Methods

IV. Conclusions and Future Perspectives

Acknowledgments

Abbreviations

References

Chapter 3: Photoactive Metal Nitrosyl and Carbonyl Complexes Derived from Designed Auxiliary Ligands: An Emerging Class of Photochemotherapeutics

I. Introduction

II. Metal Nitrosyl and Carbonyl Complexes as Nitric Oxide and Carbon Monoxide Donors

III. Photoactive Metal Nitrosyl Complexes

IV. Photoactive Metal Carbonyl Complexes

V. Conclusion

Acknowledgments

Abbreviations

References

Chapter 4: Metal—Metal Bond-Containing Complexes as Catalysts for C—H Functionalization

I. Introduction

II. Dirhodium and Diruthenium C—H Functionalization Chemistry

III. Dipalladium C—H Functionalization Chemistry

IV. Parallels Between Dirhodium and Dipalladium Systems

V. Summary

Acknowledgments

Abbreviations

References

Chapter 5: Activation of Small Molecules by Molecular Uranium Complexes

I. Introduction

II. Scope and Organization

III. Carbon Monoxide

IV. Nitrogen Monoxide

V. Dinitrogen

VI. Dioxygen

VII. Carbon Dioxide

VIII. Nitrous Oxide

IX. Water

X. Dihydrogen

XI. Saturated Hydrocarbons

XII. Alkenes and Alkynes

XIII. Arenes

XIV. Concluding Remarks

Acknowledgments

Abbreviations

References

Chapter 6: Reactive Transition Metal Nitride Complexes

I. Introduction

II. Scope

III. Previous Reviews

IV. Properties of the Nitride Ligand

V. Synthesis of Transition Metal Nitrides

VI. Reactivity

VII. Nitrides as Catalyst Precursors and Intermediates

VIII. Strategies for Increasing Nitride Reactivity

IX. Conclusions

Acknowledgments

Abbreviations

References

Subject Index

Cumulative Index

End User License Agreement

List of Tables

Table I

Table II

Table III

Table IV

Table V

Table VI

Table VII

Table VIII

Table IX

Table X

Table XI

Table XII

Table XIII

Table XIV

Table XV

Table XVI

Chart 1

Table I

List of Illustrations

Scheme 1

Figure 1

Scheme 2

Figure 2

Figure 3

Scheme 3

Figure 4

Figure 5

Figure 6

Scheme 4

Figure 7

Figure 8

Scheme 5

Figure 9

Scheme 6

Figure 10

Scheme 7

Scheme 8

Figure 11

Figure 12

Scheme 9

Figure 13

Scheme 10

Figure 14

Figure 15

Figure 16

Figure 17

Figure 18

Figure 19

Figure 20

Figure 21

Figure 22

Figure 23

Figure 24

Figure 25

Figure 26

Scheme 11

Figure 27

Figure 28

Figure 29

Figure 30

Figure 31

Figure 32

Figure 33

Figure 34

Figure 35

Figure 36

Figure 37

Figure 38

Figure 39

Figure 40

Figure 41

Figure 42

Figure 43

Figure 44

Figure 45

Figure 46

Figure 47

Figure 48

Figure 49

Figure 50

Figure 51

Figure 52

Figure 53

Figure 54

Figure 55

Figure 56

Figure 57

Figure 58

Figure 59

Figure 60

Figure 61

Figure 62

Figure 63

Figure 64

Figure 65

Figure 66

Figure 67

Figure 68

Scheme 1

Figure 1

Scheme 2

Scheme 3

Scheme 4

Scheme 5

Scheme 6

Scheme 7

Scheme 8

Scheme 9

Scheme 10

Scheme 11

Scheme 12

Scheme 13

Scheme 14

Figure 2

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Figure 11

Figure 12

Figure 13

Figure 14

Figure 15

Figure 16

Figure 17

Figure 18

Scheme 1

Scheme 2

Scheme 3

Scheme 4

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Scheme 5

Scheme 6

Scheme 7

Figure 7

Figure 8

Figure 9

Figure 10

Scheme 8

Scheme 9

Scheme 10

Scheme 11

Scheme 12

Scheme 13

Scheme 14

Scheme 15

Scheme 16

Scheme 17

Scheme 18

Scheme 19

Scheme 20

Scheme 21

Scheme 22

Scheme 23

Scheme 24

Scheme 25

Scheme 26

Scheme 27

Scheme 28

Scheme 29

Scheme 30

Scheme 31

Scheme 32

Figure 11

Scheme 33

Scheme 34

Scheme 35

Figure 12

Scheme 36

Scheme 37

Scheme 38

Scheme 39

Scheme 1

Figure 1

Figure 2

Scheme 2

Scheme 3

Scheme 4

Figure 3

Scheme 5

Figure 4

Figure 5

Figure 6

Figure 7

Scheme 6

Scheme 7

Scheme 8

Scheme 9

Scheme 10

Scheme 11

Figure 8

Scheme 12

Scheme 13

Figure 9

Figure 10

Figure 11

Scheme 14

Scheme 15

Scheme 16

Scheme 17

Figure 12

Scheme 18

Figure 13

Figure 14

Figure 15

Scheme 19

Scheme 20

Scheme 21

Figure 16

Scheme 22

Figure 17

Scheme 23

Figure 18

Figure 19

Scheme 24

Figure 20

Scheme 25

Scheme 26

Figure 21

Figure 22

Scheme 27

Figure 23

Scheme 28

Scheme 29

Figure 24

Scheme 30

Scheme 31

Scheme 32

Figure 25

Figure 26

Scheme 33

Figure 27

Figure 28

Scheme 34

Figure 29

Scheme 35

Scheme 36

Figure 30

Scheme 37

Scheme 38

Figure 31

Scheme 39

Scheme 40

Scheme 41

Scheme 42

Scheme 43

Scheme 44

Scheme 45

Scheme 46

Scheme 47

Figure 32

Figure 33

Scheme 48

Figure 34

Figure 35

Scheme 49

Scheme 50

Figure 1

Figure 2

Figure 3

Figure 4

Scheme 1

Figure 5

Scheme 2

Figure 6

Scheme 3

Figure 7

Scheme 4

Scheme 5

Scheme 6

Figure 8

Scheme 7

Scheme 8

Scheme 9

Scheme 10

Scheme 11

Scheme 12

Scheme 13

Scheme 14

Scheme 15

Scheme 16

Scheme 17

Scheme 18

Scheme 19

Scheme 20

Guide

Cover

Table of Contents

Chapter 1

Pages

ii

iii

iv

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

55

56

57

58

59

60

61

62

63

64

65

66

67

68

69

70

71

72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

87

88

89

90

91

92

93

94

95

96

97

98

99

100

101

102

103

104

105

106

107

108

109

110

111

112

113

114

115

116

117

118

119

120

121

122

123

124

125

126

127

128

129

130

131

132

133

134

135

136

137

138

139

140

141

142

143

144

145

146

147

148

149

150

151

152

153

154

155

156

157

158

159

160

161

162

163

164

165

166

167

168

169

170

171

172

173

174

175

176

177

178

179

180

181

182

183

184

185

186

187

188

189

190

191

192

193

194

195

196

197

198

199

200

201

202

203

204

205

206

207

208

209

210

211

212

213

214

215

216

217

218

219

220

221

222

223

224

225

226

227

228

229

230

231

232

233

234

235

236

237

238

239

240

241

242

243

244

245

246

247

248

249

250

251

252

253

254

255

256

257

258

259

260

261

262

263

264

265

266

267

268

269

270

271

272

273

274

275

276

277

278

279

280

281

282

283

284

285

286

287

288

289

290

291

292

293

294

295

296

297

298

299

300

301

302

303

304

305

306

307

308

309

310

311

312

313

314

315

316

317

318

319

320

321

322

323

324

325

326

327

328

329

330

331

332

333

334

335

336

337

338

339

340

341

342

343

344

345

346

347

348

349

350

351

352

353

354

355

356

357

358

359

360

361

362

363

364

365

366

367

368

369

370

371

372

373

374

375

376

377

378

379

380

381

382

383

384

385

386

387

388

389

390

391

392

393

394

395

396

397

398

399

400

401

402

403

404

405

406

407

408

409

410

411

412

413

414

415

416

417

418

419

420

421

422

423

424

425

426

427

428

429

430

431

432

433

434

435

436

437

438

439

440

441

442

443

444

445

446

447

448

449

450

451

452

453

454

455

456

457

458

459

460

461

462

463

464

465

466

467

468

469

470

471

472

473

474

475

476

477

478

479

480

481

482

483

484

485

486

487

488

489

490

491

492

493

494

495

496

497

498

499

500

501

502

503

504

505

506

507

508

509

510

511

512

513

514

515

516

517

518

Advisory Board

JACQUELINE K. BARTON

CALIFORNIA INSTITUTE OF TECHNOLOGY, PASADENA, CALIFORNIA

SHUNICHI FUKUZUMI

OSAKA UNIVERSITY, OSAKA, JAPAN

CLARK R. LANDIS

UNIVERSITY OF WISCONSIN, MADISON, WISCONSIN

NATHAN S. LEWIS

CALIFORNIA INSTITUTE OF TECHNOLOGY, PASADENA, CALIFORNIA

STEPHEN J. LIPPARD

MASSACHUSETTS INSTITUTE OF TECHNOLOGY, CAMBRIDGE, MASSACHUSETTS

JEFFREY R. LONG

UNIVERSITY OF CALIFORNIA, BERKELEY, CALIFORNIA

THOMAS E. MALLOUK

PENNSYLVANIA STATE UNIVERSITY, UNIVERSITY PARK, PENNSYLVANIA

TOBIN J. MARKS

NORTHWESTERN UNIVERSITY, EVANSTON, ILLINOIS

JAMES M. MAYER

UNIVERSITY OF WASHINGTON, SEATTLE, WASHINGTON

DAVID MILSTEIN

WEIZMANN INSTITUTE OF SCIENCE, REHOVOT, ISRAEL

WONWOO NAM

EWHA WOMANS UNIVERSITY, SEOUL, KOREA

VIVIAN W. W. YAM

UNIVERSITY OF HONG KONG, HONG KONG

Progress in Inorganic Chemistry

Volume 58

Edited by

Kenneth D. Karlin

Department of Chemistry

Johns Hopkins University

Baltimore, Maryland

Copyright © 2014 by John Wiley & Sons, Inc. All rights reserved

Published by John Wiley & Sons, Inc., Hoboken, New Jersey

Published simultaneously in Canada

No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750–8400, fax [phone], or on the web at www.copyright.com. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, (201) 748–6011, fax [phone], or online at http://www.wiley.com/go/permission.

Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives or written sales materials. The advice and strategies contained herein may not be suitable for your situation. You should consult with a professional where appropriate. Neither the publisher nor author shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages.

For general information on our other products and services or for technical support, please contact our Customer Care Department within the United States at (800) 762–2974, outside the United States at (317) 572–3993 or fax [phone].

Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic formats. For more information about Wiley products, visit our web site at www.wiley.com.

Library of Congress Catalog Number: 59-13035

ISBN 978-1-118-79282-7

Tris(dithiolene) Chemistry: A Golden Jubilee

Stephen Sproules

West CHEM, School of Chemistry, University of Glasgow, Glasgow, G12 8QQ United Kingdom

Contents

Introduction

Ligands

Arene Dithiolates

Alkene Dithiolates

Sulfur

Carbon Disulfide

Phosphorus Pentasulfide

Other Sulfur Sources

Dithiones

Complexes

Metathesis

Redox

Transmetalation

Structures

Beginnings

Neutral Complexes

Reduced Complexes

Isoelectronic Series

Redux

Trigonal Twist

Dithiolene Fold

Oxidized Ligands

Theory

Hückel

Fenske–Hall

Electrochemistry

Magnetometry

Spectroscopy

Vibrational

Electronic

Nuclear Magnetic Resonance

Electron Paramagnetic Resonance

Spin Doublet

Spin Quartet

X-Ray Absorption Spectroscopy

Metal Edges

Sulfur K-Edge

Mössbauer

Summary

Group 4 (IV B)

Group 5 (V B)

Group 6 (VI B)

Group 7 (VII B)

Group 8 (VIII B)

Group 9 (VIII B) and Beyond

Conclusions

Acknowledgments

Abbreviations

References

I. Introduction

The search for organometallic compounds with sulfur-donor ligands gave inorganic chemistry its first tris(dithiolene) coordination compound in 1963 (1). Anticipating a combination of CO and sulfur-donor ligands, King (1) apathetically described the product of the reaction of bis(trifluoromethyl)dithiete with molybdenum hexacarbonyl as a hexavalent metal coordinated to three as yet unidentified dithiols. The first bis(dithiolene) homologues with late transition metals appeared in the literature the previous year (2,3). Seduced by the remarkable properties exhibited by these compounds, three research groups led the investigation in the early 1960s: Gray and his cohort at Columbia and then at Caltech; Schrauzer and co-workers in Munich, the Shell Development Company, and University of California at San Diego; and finally the Harvard quartet of Davison, Edelstein, Holm, and Maki. The competitive environment that ensued significantly advanced this emerging field into what we now know as transition metal dithiolene chemistry. Bis(dithiolene) compounds elicited greater interest than their tris(dithiolene) analogues despite both being strongly chromophoric, exhibiting multiple reversible electron-transfer processes, and possessing unprecedented molecular geometries. Bis(dithiolenes) were found to be persistently square planar (3–5), an outcome that could only arise from ligand participation in the frontier orbitals. Therefore, this sulfur–donor ligand with an unsaturated carbon backbone is regarded as the first noninnocent chelating ligand as it can exist in one of three forms: a dianionic dithiolate, a monoanionic dithienyl radical, and a neutral dithione (Scheme 1). Gray and co-workers (6,7) worked on the premise that these were metal stabilized radical-ligand systems. Schrauzer and co-workers (8,9) could never escape calling these dithioketones, whereas Holm, Maki, and co-workers (4,10) avoided applying such definitive terms. An innovative compromise was brokered by McCleverty (11,12) when he introduced the term dithiolene, obviating the need to specifiy discrete oxidation levels (13,14). Only the metal was assigned, and for the archetypal bis(dithiolene) complexes of group 10 (VIII B) metals, it was unanimously agreed that a low-spin d ion lay at the center of the neutral, monoanionic, and dianionic species, with each differing in the occupation of ligand-based valence orbitals.