Vibrational Spectra of Organometallics
Theoretical and Experimental Data

A comprehensive compilation of the available experimental and theoretical vibrational data for organometallic compounds and its role in evaluating the structures, bonding, and properties of these key compounds

This unique book offers a thorough review of the literature dealing with vibrational data obtained using various phases, including matrices, reported for organometallic compounds from infrared spectra, Raman spectra, and several other techniques. It is the only one that compiles the available experimental and theoretical vibrational data on these compounds, and which discusses the importance of this information and its role in evaluating structures, bonding, and other important properties. It also treats the use of DFT and other theoretical calculations to analyze the vibrational data and to predict properties associated with these compounds. The book also includes vibrational data for organic species that form on metal and other surfaces.

Vibrational Spectra of Organometallics: Theoretical and Experimental Data offers complete coverage of: Carbide, Alkylidyne, Alkylidene, Alkyl, and Alkane Derivatives; Noncyclic Carbon Clusters and Unsaturated Hydrocarbon Derivatives; and Cyclic, Unsaturated Organometallic Derivatives. By summarizing work that has already been done on organometallic compounds, it serves as an important reference for those studying their vibrational spectra and will, in the end, lead to a clearer understanding of other research that needs to be done in order to help researchers determine new research directions.

• An important reference for those studying the vibrational spectra of organometallic compounds
• Gathers the existing experimental and theoretical vibrational data and discusses its significance in assessing structures, bonding, and other principle properties
• Includes DFT methods for the interpretation of spectra, which has been one of the major developments of the last two decades 

Vibrational Spectra of Organometallics: Theoretical and Experimental Data is an important reference for researchers and practitioners in the areas of inorganic, organometallic, organic, and surface chemistry who have an interest in using vibrational data to characterize the bonding, composition, reactions, and structures of organometallic compounds, and organic species that are formed on various surfaces.

Preface xi

Part I Carbide, Alkylidyne, Alkylidene, Alkyl, and Alkane Compounds 1

1 Monocarbide Complexes 3

2 Terminal and Bridging Methylidyne (CH) and Other Alkylidyne Complexes 9

3 Terminal and Bridging Methylidene (CH₂) and Other Alkylidene Complexes 13

4 Methyl Complexes 21

4.1 Neutral Monomeric Complexes 21

4.2 Cationic and Anionic Monomeric Complexes 29

4.3 Bridged Methyl Complexes 33

5 Methane and Other Alkane Complexes 37

6 Terminal and Bridged Ethyl Complexes 43

7 Propyl, Butyl, and Pentyl Complexes 49

8 Cycloalkyl and Cycloalkane Complexes 53

9 Saturated Heterometallacycle Complexes 55

10 Benzyl Complexes 59

11 Mixed Alkyl and Alkyl–Aryl Complexes 61

12 Surface Bound Alkyl, Alkane, and Alkyl–Metal Complexes 63

12.1 Metal Surfaces 63

12.2 Metalloid Surfaces 65

12.3 Inorganic Oxide Surfaces 66

13 Alkyl, Alkylidyne, and Alkylidene Complexes with Other Functional Groups 69

13.1 Hydrides 69

13.2 Halides and Mixed Halides and Hydrides 84

13.3 Pseudohalides 120

13.4 Carbonyl and Dinitrogen Complexes 135

13.5 Diazomethane (CH₂N⁺=N⁻) and Related Complexes 139

13.6 Organic Isocyanides (Isonitriles, R‐N≡C), Organic Nitriles (R‐C≡N) and Iminoacyl Complexes 139

13.7 Carbon Dioxide and Carbon Disulfide Complexes 141

13.8 Aqua, Hydroxide, Oxide, Peroxide, and Oxyhalide Complexes 146

13.9 Hydrogen Sulfide, Mercaptide, Sulfide, and Disulfide Complexes 161

13.10 Alkoxide, Organoperoxide, Ether, and Alcohol Complexes 164

13.11 Alkylsulfide, Dialkylsulfide, and Methanethiol Complexes 171

13.12 Carboxylate, Thiocarboxylate, Dithiocarboxylate, and Xanthate Complexes 173

13.13 Formaldehyde, Formyl, Acetaldehyde, Acyl, and Related Complexes 180

13.14 Ketone, Ketenyl, and Related Complexes 187

13.15 β‐Diketonate and Related Complexes 190

13.16 Nitrogen Bases and Miscellaneous Lewis‐Base and Chelating Ligands 195

14 Complexes with Metal–Metal Bonds 215

14.1 Homonuclear Bonds 215

14.2 Heteronuclear Bonds 219

15 Halogenated Alkyl Complexes 225

15.1 Main Group Elements 225

15.2 Transition and Actinide Elements 234

Part I References 241

Part II Noncyclic Carbon-Clusters and Unsaturated Hydrocarbon Compounds 299

16 Linear Carbon Cluster Complexes 301

16.1 C₂ Complexes 301

16.2 C₃ Complexes 304

16.3 C₄ Complexes 304

16.4 C₅ and Larger Complexes 305

17 Ethynyl, Ethyne, and Related Complexes 309

17.1 Main Group Elements 309

17.2 d and f Block Elements 319

18 Vinyl and Vinylidene Complexes 343

19 Ethene and Related Monoalkene Complexes 355

20 Allyl and Related Complexes 371

21 Allene and Related Complexes 387

22 Conjugated and Nonconjugated Diolefin and Related Complexes 391

22.1 Butadiene and Butatriene Complexes 391

22.2 Pentadiene Complexes 396

22.3 Hexadiene Complexes 398

22.4 Miscellaneous Olefin Complexes 399

Part II References 403

Part III Cyclic, Unsaturated Organometallic Compounds 427

23 Metal Complexes of Fullerenes and Other Nonlinear Carbon Clusters 429

24 Three‐carbon Rings 433

25 Four‐carbon Rings 435

26 Five‐carbon Rings 441

26.1 Cyclopentene and Cyclopentyl Complexes 441

26.2 1,3‐Cyclopentadiene, Cyclopentadienone, and Related Complexes 441

26.3 Anionic Cyclopentadienide Complexes 443

26.4 Covalent Cyclopentadienyl Complexes 446

27 Six‐carbon Rings 547

27.1 Cyclohexene Complexes 547

27.2 Cyclohexadiene, Cyclohexadienyl, Oxocyclohexadienyl, and Quinone Complexes 547

27.3 Neutral, Cationic, and Anionic Phenyl Complexes 550

27.4 Phenyl Compounds with Other Functional Groups 559

27.5 Phenyl Complexes with Metal–Metal Bonds 585

27.6 Ring‐Substituted Phenyl Complexes 588

27.7 Perhalogenated Phenyl Complexes 591

27.8 Benzene Ring Complexes 596

27.9 Ring‐Substituted Benzene Complexes 608

27.10 Benzyne Complexes 611

28 Seven‐carbon Rings 613

29 Eight‐carbon Rings 615

30 Nine‐carbon Rings 629

31 Ten‐carbon Rings 631

32 Coupled Organic Ring Complexes 633

33 Fused Organic Ring Complexes 635

33.1 Pentalenyl Complexes 635

33.2 Indene and Indenyl Complexes 635

33.3 Fluorene and Fluorenyl Complexes 641

33.4 Indacenyl Complexes 641

33.5 Azulene Complexes 641

33.6 Naphthalene and Larger Fused Aromatic Ring Complexes 642

34 Miscellaneous Cyclic Olefin and Mixed Ring Complexes 643

35 Carboranes and Metallacarboranes 647

36 Five‐ and Six‐membered Heterocyclic Rings and Their Metal Complexes 651

37 Unsaturated Metallacycle Rings with Four or More Atoms 657

Part III References 661

Index 709

Edward Maslowsky, Jr., Ph.D., is Professor Emeritus of Chemistry in the Division of Molecular, Life, and Health Science at Loras College, Dubuque, Iowa, USA.