Infrared and Raman Spectra of Inorganic and Coordination Compounds FOURTH EDITION ‘gy 37 KAZUO NAKAMOTO Wehr Professor of Chemistry Marquette University 4 menooices” [A Wiley-Interscience Publication JOHN WILEY & SONS New York © Chichester * Brisbane * Toronto * Singapore‘A. Bruha of Marquette University, who proofread the reference sections, and to the publishers and colleagues Who gave me permission to reproduce some figures in this book. Finally, 1 would like to thank the National Science Foundation, which provided continuing support far my research during the preparation of this edition. Kazuo NAKAMOTO Mawaudee, Wisconsin May 1986 Contents List of Abbreviations xi Part I. Theory of Normal Vibration 1 12 13 4 15 16 7 1s. 1 1410 a 12 13 Lid 15 116 17 118" 1s 120 2 122 123 Refer Origin of Molecular Spectra 3 ~Vibrtion of « Diatomic Molecule 9 Normal Coordinates and Normal Vibrations 12 Symmetry Elements and Point Groups 18 Symmetry of Normal Vibrations and Selection Rules 20 Introduction to Group Theory 25 ‘The Number of Normal Vibrations for Each Species 29 Internal Coordinates 36 Selection Rules for Infrared and Raman Spectsa 39 Structure Determination 44 Principle of the GF Matcix Method 46 Usilization of Symmetry Properties 52 Potential Fields and Force Constants $7 of the Secular Equation 59 ational Frequenics of owopie Molecules 62 Metal-Isotope Specttoscopy 63 Group Frequencies and Band Assignments 66 Intensity of Infrared Absorption 70 Depolarization of Raman Lines _72 Intensity of Raman Seattering 76 Resonance Raman Specira 78 Vibration Spectra in Gaseous Phase and Inert Gas Matices 83 Vibrational Spectra of Crystals $6 ences 94viii conTENTS Part II. Inorganic Compounds et m2 13 14 1s 116 17 18. 19 40 TW 112 Diatomie Molecules 101 ‘Triatomic Molecules 108 Pyramidal Four-Atom Molecules 115 Planar Four-Atom Molecules 121 Other Four-Atom Molecules 125 Tetrahedral and Square-Planar Five-Atom Molecules 130 ‘Trigonal-Bipyramidal and Tetragonal-Pyramidal XY; and Related Molecules 144 Octahedral Molecules 147 XY; and XY, Molecules 156 X,Y, and X;¥, Molecules 158 XY), KaYu, XaYo, and XYio Molecules 165 Compounds of Other Types 167 References 169) Part IIT. Coordination Compounds, met m2 ms m4 MES M16 m7 m8 m9 M10 mE mE 3 m4 MILs 6 m7 OB m9 111-20 M121 11-22 Ammine, Amido, and Related Complexes 191 Complexes of Ethylenediamine and Related Compounds 201 Complexes of Pyridine, Bipyridine, and Related Com: pounds 206 Metalloporphyrins and Related Compounds 213 iro and Nitto Complexes 221 Lattice Water and Aquo and Hydroxo Complexes 227 Complexes of Alcohols, Ethers, Ketones, Aldehydes, Esters, and Carboxylic Acids 231 Complexes of Amino Acids, EDTA, and Related Com: pounds 233 Infrared Spectra of Aqueous Solutions 239 Complexes of Oxalic Acid and Related Compounds 244 Sulfato, Carbonato, and Other Acido Complexes 248 Complexes of f-Diketones 259 Complexes of Urea, Sulfoxides, and Related Compounds 268 Cyano and Nitrile Complexes "272 ‘Thiocyanato and Other Pseudohalogeno Complexes 282 Carbonyl and Nitrosyl Complexes 291 Complexes of Dioxygen (O,) 310 Dinitrogen(N;), Nitrido(N), and Hydrido(H) Complexes 320 Halogeno Complexes 324 Complexes Containing Metal-Metal Bonds 331 Complexes of Phosphines and Arsines 338 Complexes of Sulfur-, Selenium-, and Tellusium-Containing Ligands 342 References 349 Part IV. Organometallic Compounds IVI Metal Alkanes 375 1-2 Metal Alkenes, Alkynes, and Phenyls 378 IV-3 Halogeno and Pscudohslogeno Compounds 379 1V-4 Compounds Containing Other Functional Groups 383 IV-5 Complexes of Alkenes, Alkynes, and Related Ligands 386 1V-6 Cyclopentadienyl Complexes 391 IV-7 Cyclopentadienyl Compounds Containing Other Groups 395 IV-8 Complexes of Other Cyclic Unsaturated Ligands 400 IV-9 Miscellaneous Compounds 403 References 403 Part V. Bioinorganic Compounds V-1 Myoglobin and Hemoglobin 414 V2 Cytochromes and Other Heme Proteins 422 V-3 Hemerythrins 426 V-4 Hemocyanins 430 V-5 Blue Copper Proteins 434 V-6 Iron-Sulfur Proteins 436 References 445 Appendixes mL Vv v v Point Groups and Their Character Tables 450 General Formulas for Calculating the Number of Normal Vibrations in Bach Species 458 Number of Infrared- and Raman-Active Stretching Vibrations for MX,Yn-Type Molecules 454 Derivation of Eq. 11.3 (Part I) 465 The G and F Matrix Elements of Typical Molecules 467 Group Frequency Charts 472 479