Inorganic chemistry 6e by shriver, weller

18 PERIODIC TABLE OF THE ELEMENTS VIII VIIA Group I II IA IIA 3 Period 13 1.0079 1s1 Be 15 14 16 4.00 1s2 helium III IV V VI VII IIIA IVA VA VIA VIIA B C N O He 17 F 10 Ne beryllium boron carbon nitrogen oxygen fluorine neon 6.94 2s1 9.01 2s2 10.81 2s22p1 12.01 2s22p2 14.01 2s22p3 16.00 2s22p4 19.00 2s22p5 20.18 2s22p6 11 Na 13 magnesium alumin ium silicon phosphorus sulf ur chlorine argon 22.99 3s1 24.31 3s2 26.98 3s23p1 28.09 3s23p2 30.97 3s23p3 32.06 3s23p4 35.45 3s23p5 39.95 3s23p6 33 IVB VB VIB VIIB 10 11 12 IB IIB VIIIB P 15 16 17 18 Ar 31 Ga 32 Ge tit anium vanadium chromium manganese iron cobalt nickel copper zinc gallium germa nium arsenic selenium bromine krypton 39.10 4s1 40.08 4s2 44.96 3d14s2 47.87 3d24s2 50.94 3d34s2 52.00 3d54s1 54.94 3d54s2 55.84 3d64s2 58.93 3d74s2 58.69 3d84s2 63.55 3d104s1 65.41 3d104s2 69.72 4s24p1 72.64 4s24p2 74.92 4s24p3 78.96 4s24p4 79.90 4s24p5 83.80 4s24p6 37Rb 38 Pd 47 Ag 48 Sb 52 Te 21 Sc 22 Ti 23 V 24 25 Mn Fe 27 Co 28 Ni Zr 41 Nb 42 Mo 43 rubidium st rontium yttrium zirconium niobium molybde num technetium 85.47 5s1 87.62 5s2 88.91 4d15s2 91.22 4d25s2 92.91 4d45s1 95.94 4d55s1 (98) 4d55s2 101.07 102.90 106.42 4d75s1 4d85s1 4d10 55 Cs 56 57 La 72 W 75 Re 76 caesium 132.91 6s1 Sr Ba barium 39 Y lanthan um 137.33 138.91 6s2 5d16s2 88 Ra 40 89 Ac Hf 73 hafnium 178.49 5d26s2 104 Rf Ta tantalum 74 Tc 26 rhenium tungsten 180.95 183.84 5d36s2 5d46s2 44 Ru ruthenium Os osmium 45 Rh rhodium 77 Ir iridium 46 palladium 78 Pt 186.21 190.23 192.22 195.08 5d76s2 5d56s2 5d66s2 5d96s1 105Db 106 Sg 107 Bh 108 Hs 109 Mt 110 Ds radium act inium rutherfordium dubnium sea borgium bohrium hassium meit nerium darmstadtium (223) 7s1 (226) 7s2 (227) 6d17s2 (261) 6d27s2 (262) 6d37s2 (266) 6d47s2 (264) 6d57s2 (277) 6d67s2 (268) 6d77s2 (271) 6d87s2 58 Ce cerium 140.12 4f15d16s2 59 Pr Nd neo dymiu m 61 Pm 62 Sm promethium samarium Cd cadmium 49 In Sn 50 indium tin Au Hg 196.97 200.59 204.38 5d106s1 5d106s2 6s26p1 207.2 6s26p2 208.98 6s26p3 (209) 6s26p4 (210) 6s26p5 (222) 6s26p6 111 Rg 112 Cp 114 Fl 113 83 115 116 Lv copernicum flerovium livermorium (272) (277) 6d107s1 6d107s2 (289) 7s27p2 (293) 7s27p4 roentgenium Eu 64 Gd gad olinium 65 Tb 66 Dy 67 Ho 68 Er 69 Tm holmium erbium thulium 94 Pu 95 Am 96 Cm 97 Bk 98 pluton ium americium curium berkelium califo rn iu m eins teinium 231.04 238.03 (237) 5f46d17s2 (243) 5f77s2 (247) 5f26d17s2 5f36d17s2 (244) 5f67s2 (247) 5f97s2 (251) 5f107s2 (252) 5f117s2 U uranium xenon 126.90 131.29 5s25p5 5s25p6 radon nep tu nium 92 54 Xe iodine astatine 82 Pb thallium 93 Np 91 Pa I Kr polonium 81 162.50 4f106s2 protactinium 53 36 84 Po mercury Tl Br Bi 80 158.93 4f96s2 thorium tellurium 35 bismuth gold 150.36 151.96 157.25 4f66s2 4f76s2 4f75d16s2 (145) 4f56s2 antimony Se lead 79 dysprosium 140.91 144.24 4f36s2 4f46s2 51 34 107.87 112.41 114.82 118.71 121.76 127.60 5s25p2 5s25p3 5s25p4 4d105s1 4d105s2 5s25p1 europ iu m 63 Zn 30 terbium praseodymium 90 Th 232.04 6d27s2 60 silver platinum francium Molar masses (atomic weights) quoted to the number of significant figures given here can be regarded as typical of most naturally occuring samples- 29 Cu As S scandium 20 Cr 14 calcium K po tassium Ca IIIB Al Si Cl 12 Mg sodium 87 Fr H hydrogen Period lithium 19 Li 5f76d17s2 Cf 164.93 167.26 4f116s2 4f126s2 99 Es 70 85 At 86 118 117 Yb Rn 71 Lu Lanthanoids 168.93 173.04 174.97 (lanthanides) 4f136s2 4f146s2 5d16s2 ytterbium lutetium 100Fm 101Md 102 No 103 Lr fermium me ndelev ium nobelium (257) 5f127s2 (258) 5f137s2 (259) 5f147s2 Act inoids (262) (actinides) 6d17s2 lawrencium The elements Name Symbol Atomic number Molar mass (g mol−1) Name Symbol Atomic number Molar mass (g mol−1) Actinium Aluminium (aluminum) Americium Antimony Argon Arsenic Astatine Barium Berkelium Beryllium Bismuth Bohrium Boron Bromine Cadmium Caesium (cesium) Calcium Californium Carbon Cerium Chlorine Chromium Cobalt Copernicum Copper Curium Darmstadtium Dubnium Dysprosium Einsteinium Erbium Europium Fermium Flerovium Fluorine Francium Gadolinium Gallium Germanium Gold Hafnium Hassium Helium Holmium Hydrogen Indium Iodine Iridium Iron Krypton Lanthanum Lawrencium Lead Lithium Livermorium Lutetium Magnesium Ac Al Am Sb Ar As At Ba Bk Be Bi Bh B Br Cd Cs Ca Cf C Ce Cl Cr Co Cp Cu Cm Ds Db Dy Es Er Eu Fm Fl F Fr Gd Ga Ge Au Hf Hs He Ho H In I Ir Fe Kr La Lr Pb Li Lv Lu Mg 89 13 95 51 18 33 85 56 97 83 107 35 48 55 20 98 58 17 24 27 112 29 96 110 105 66 99 68 63 100 114 87 64 31 32 79 72 108 67 49 53 77 26 36 57 103 82 116 71 12 227 26.98 243 121.76 39.95 74.92 210 137.33 247 9.01 208.98 264 10.81 79.90 112.41 132.91 40.08 251 12.01 140.12 35.45 52.00 58.93 277 63.55 247 271 262 162.50 252 167.27 151.96 257 289 19.00 223 157.25 69.72 72.64 196.97 178.49 269 4.00 164.93 1.008 114.82 126.90 192.22 55.84 83.80 138.91 262 207.2 6.94 293 174.97 24.31 Manganese Meitnerium Mendelevium Mercury Molybdenun Neodymium Neon Neptunium Nickel Niobium Nitrogen Nobelium Osmium Oxygen Palladium Phosphorus Platinum Plutonium Polonium Potassium Praseodymium Promethium Protactinium Radium Radon Rhenium Rhodium Roentgenium Rubidium Ruthenium Rutherfordium Samarium Scandium Seaborgium Selenium Silicon Silver Sodium Strontium Sulfur Tantalum Technetium Tellurium Terbium Thallium Thorium Thulium Tin Titanium Tungsten Uranium Vanadium Xenon Ytterbium Yttrium Zinc Zirconium Mn Mt Md Hg Mo Nd Ne Np Ni Nb N No Os O Pd P Pt Pu Po K Pr Pm Pa Ra Rn Re Rh Rg Rb Ru Rf Sm Sc Sg Se Si Ag Na Sr S Ta Tc Te Tb TI Th Tm Sn Ti W U V Xe Yb Y Zn Zr 25 109 101 80 42 60 10 93 28 41 102 76 46 15 78 94 84 19 59 61 91 88 86 75 45 111 37 44 104 62 21 106 34 14 47 11 38 16 73 43 52 65 81 90 69 50 22 74 92 23 54 70 39 30 40 54.94 268 258 200.59 95.94 144.24 20.18 237 58.69 92.91 14.01 259 190.23 16.00 106.42 30.97 195.08 244 209 39.10 140.91 145 231.04 226 222 186.21 102.91 272 85.47 101.07 261 150.36 44.96 266 78.96 28.09 107.87 22.99 87.62 32.06 180.95 98 127.60 158.93 204.38 232.04 168.93 118.71 47.87 183.84 238.03 50.94 131.29 173.04 88.91 65.41 91.22 this page left intentionally blank Sixth Edition Duward Shriver Northwestern University Mark Weller University of Bath Tina Overton University of Hull Jonathan Rourke University of Warwick Fraser Armstrong University of Oxford Publisher: Jessica Fiorillo Associate Director of Marketing: Debbie Clare Associate Editor: Heidi Bamatter Media Acquisitions Editor: Dave Quinn Marketing Assistant: Samantha Zimbler Library of Congress Preassigned Control Number: 2013950573 ISBN-13: 978–1–4292–9906–0 ISBN-10: 1–4292–9906–1 ©2014, 2010, 2006, 1999 by P.W Atkins, T.L Overton, J.P Rourke, M.T Weller, and F.A Armstrong All rights reserved Published in Great Britain by Oxford University Press This edition has been authorized by Oxford University Press for sale in the United States and Canada only and not for export therefrom First printing W H Freeman and Company 41 Madison Avenue New York, NY 10010 www.whfreeman.com Preface Our aim in the sixth edition of Inorganic Chemistry is to provide a comprehensive and contemporary introduction to the diverse and fascinating subject of inorganic chemistry Inorganic chemistry deals with the properties of all of the elements in the periodic table These elements range from highly reactive metals, such as sodium, to noble metals, such as gold The nonmetals include solids, liquids, and gases, and range from the aggressive oxidizing agent fluorine to unreactive gases such as helium Although this variety and diversity are features of any study of inorganic chemistry, there are underlying patterns and trends which enrich and enhance our understanding of the discipline These trends in reactivity, structure, and properties of the elements and their compounds provide an insight into the landscape of the periodic table and provide a foundation on which to build a detailed understanding Inorganic compounds vary from ionic solids, which can be described by simple applications of classical electrostatics, to covalent compounds and metals, which are best described by models that have their origin in quantum mechanics We can rationalize and interpret the properties and reaction chemistries of most inorganic compounds by using qualitative models that are based on quantum mechanics, such as atomic orbitals and their use to form molecular orbitals Although models of bonding and reactivity clarify and systematize the subject, inorganic chemistry is essentially an experimental subject New inorganic compounds are constantly being synthesized and characterized through research projects especially at the frontiers of the subject, for example, organometallic chemistry, materials chemistry, nanochemistry, and bioinorganic chemistry The products of this research into inorganic chemistry continue to enrich the field with compounds that give us new perspectives on structure, bonding, reactivity, and properties Inorganic chemistry has considerable impact on our everyday lives and on other scientific disciplines The chemical industry is strongly dependent on it Inorganic chemistry is essential to the formulation and improvement of modern materials such as catalysts, semiconductors, optical devices, energy generation and storage, superconductors, and advanced ceramics The environmental and biological impacts of inorganic chemistry are also huge Current topics in industrial, biological, and sustainable chemistry are mentioned throughout the book and are developed more thoroughly in later chapters In this new edition we have refined the presentation, organization, and visual representation All of the book has been revised, much has been rewritten, and there is some completely new material We have written with the student in mind, including some new pedagogical features and enhancing others The topics in Part 1, Foundations, have been updated to make them more accessible to the reader with more qualitative explanation accompanying the more mathematical treatments Some chapters and sections have been expanded to provide greater coverage, particularly where the fundamental topic underpins later discussion of sustainable chemistry Part 2, The elements and their compounds, has been substantially strengthened The section starts with an enlarged chapter which draws together periodic trends and cross references forward to the descriptive chapters An enhanced chapter on hydrogen, with reference to the emerging importance of the hydrogen economy, is followed by a series of chapters traversing the periodic table from the s-block metals through the p block to the Group 18 gases Each of these chapters is organized into two sections: The essentials describes the fundamental chemistry of the elements and The detail provides a more thorough, in-depth account This is followed by a series of chapters discussing the fascinating chemistry of the d-block and, finally, the f-block elements The descriptions of the chemical properties of each group of elements and their compounds are enriched with illustrations of current research and applications The patterns and trends that emerge are rationalized by drawing on the principles introduced in Part Part 3, Frontiers, takes the reader to the edge of knowledge in several areas of current research These chapters explore specialized subjects that are of importance to industry, materials science, and biology, and include catalysis, solid state chemistry, nanomaterials, metalloenzymes, and inorganic compounds used in medicine vi Preface We are confident that this text will serve the undergraduate chemist well It provides the theoretical building blocks with which to build knowledge and understanding of inorganic chemistry It should help to rationalize the sometimes bewildering diversity of descriptive chemistry It also takes the student to the forefront of the discipline with frequent discussion of the latest research in inorganic chemistry and should therefore complement many courses taken in the later stages of a program Acknowledgments We have taken care to ensure that the text is free of errors This is difficult in a rapidly changing field, where today's knowledge is soon replaced by tomorrow’s Many of the figures in Chapters 26 and 27 were produced using PyMOL software (W.L DeLano, The PyMOL Molecular Graphics System, DeLano Scientific, San Carlos, CA, USA, 2002) We thank colleagues past and present at Oxford University Press—Holly Edmundson, Jonathan Crowe, and Alice Mumford—and at W H Freeman—Heidi Bamatter, Jessica Fiorillo, and Dave Quinn—for their help and support during the writing of this text Mark Weller would also like to thank the University of Bath for allowing him time to work on the text and numerous illustrations We acknowledge and thank all those colleagues who so willingly gave their time and expertise to a careful reading of a variety of draft chapters Mikhail V Barybin, University of Kansas Deborah Kays, University of Nottingham Byron L Bennett, Idaho State University Susan Killian VanderKam, Princeton University Stefan Bernhard, Carnegie Mellon University Michael J Knapp, University of Massachusetts – Amherst Wesley H Bernskoetter, Brown University Georgios Kyriakou, University of Hull Chris Bradley, Texas Tech University Christos Lampropoulos, University of North Florida Thomas C Brunold, University of Wisconsin – Madison Simon Lancaster, University of East Anglia Morris Bullock, Pacific Northwest National Laboratory John P Lee, University of Tennessee at Chattanooga Gareth Cave, Nottingham Trent University Ramón López de la Vega, Florida International University David Clark, Los Alamos National Laboratory Yi Lu, University of Illinois at Urbana-Champaign William Connick, University of Cincinnati Joel T Mague, Tulane University Sandie Dann, Loughborough University Andrew Marr, Queen’s University Belfast Marcetta Y Darensbourg, Texas A&M University Salah S Massoud, University of Louisiana at Lafayette David Evans, University of Hull Charles A Mebi, Arkansas Tech University Stephen Faulkner, University of Oxford Catherine Oertel, Oberlin College Bill Feighery, IndianaUniversity – South Bend Jason S Overby, College of Charleston Katherine J Franz, Duke University John R Owen, University of Southampton Carmen Valdez Gauthier, Florida Southern College Ted M Pappenfus, University of Minnesota, Morris Stephen Z Goldberg, Adelphi University Anna Peacock, University of Birmingham Christian R Goldsmith, Auburn University Carl Redshaw, University of Hull Gregory J Grant, University of Tennessee at Chattanooga Laura Rodríguez Raurell, University of Barcelona Craig A Grapperhaus, University of Louisville Professor Jean-Michel Savéant, Université Paris Diderot – Paris P Shiv Halasyamani, University of Houston Douglas L Swartz II, Kutztown University of Pennsylvania Christopher G Hamaker, Illinois State University Jesse W Tye, Ball State University Allen Hill, University of Oxford Derek Wann, University of Edinburgh Andy Holland, Idaho State University Scott Weinert, Oklahoma State University Timothy A Jackson, University of Kansas Nathan West, University of the Sciences Wayne Jones, State University of New York – Binghamton Denyce K Wicht, Suffolk University About the book Inorganic Chemistry provides numerous learning features to help you master this wideranging subject In addition, the text has been designed so that you can either work through the chapters chronologically, or dip in at an appropriate point in your studies The text’s Book Companion Site provides further electronic resources to support you in your learning The material in this book has been logically and systematically laid out, in three distinct sections Part 1, Foundations, outlines the underlying principles of inorganic chemistry, which are built on in the subsequent two sections Part 2, The elements and their compounds, divides the descriptive chemistry into ‘essentials’ and ‘detail’, enabling you to easily draw out the key principles behind the reactions, before exploring them in greater depth Part 3, Frontiers, introduces you to exciting interdisciplinary research at the forefront of inorganic chemistry The paragraphs below describe the learning features of the text and Book Companion Site in further detail Organizing the information Key points The key points outline the main take-home message(s) of the section that follows These will help you to focus on the principal ideas being introduced in the text Context boxes Context boxes demonstrate the diversity of inorganic chemistry and its wide-ranging applications to, for example, advanced materials, industrial processes, environmental chemistry, and everyday life Further reading Each chapter lists sources where further information can be found We have tried to ensure that these sources are easily available and have indicated the type of information each one provides Resource section At the back of the book is a comprehensive collection of resources, including an extensive data section and information relating to group theory and spectroscopy Notes on good practice In some areas of inorganic chemistry the nomenclature commonly in use today can be confusing or archaic—to address this we have included short “notes on good practice” that make such issues clearer for the student Index 1,1-migratory insertion reaction, 619 1,2-insertion reaction, 620 16-electron complex, 581 18-electron complex, 581 18-electron rule, 581 5f orbitals in covalent bonding, 646 ab initio methods, 56 absorption spectroscopy, 239 acetylides, 399 acid ionization constant, 118 acid phosphatase, 792 acid rain, 447 acid–base catalysis by metalloenzymes, 788 acid–base discrimination window, 143 acid–base reaction, 116 acidic and basic oxides, 129 acidic solvents, 146 acidity constant, 118, 121 (Table) acids, 116 acids and bases: strengths, 120 aconitase, 793 actinoid metals: properties and uses, 627 actinoids, 625 electron configurations and oxidation states, 644 electronic spectra, 647 Frost diagrams, 645 general trends, 643 half-lives, 628 occurrence and recovery, 627 separation by ion exchange, 644 actinyl unit (AnO22+): molecular orbital diagram, 646 activated carbon, 389 activation: entropy of, 559 volume of, 559 adenosine pyrophosphate, 443 adenosine triphosphate, 131, 413, 427, 767 synthesis, 784 adenosine diphosphate, 131 ADP, see adenosine diphosphate AFM, see atomic force microscopy Ag2HgI4, 661 agate, 382 AgI, 83 agostic hydrogen, 597 Al2O3, 667 albite, 402 ALD, see atomic layer deposition algaecides, 405 alkali metal halides, 324 alkaline earth metals, 336 alkane ligand, 597 alkene epoxidation, 754 alkylaluminium, 377 alkylarsanes, 429 alkylboranes, 377 alkylidene, 597 alkyltin, 405 allotropes, 356, 359, 382, 409 allowed transition, 542 alloy, 72, 76, 358, 360, 383 allyl ligand, 594 alternation effect, 276, 355 alumina, 743 aluminium, 354 hydride, 358 hydrides, 374 hydroxide, 376 monohalides, 375 organo compounds, 377 oxide, 358 oxo compounds, 376 phosphate frameworks, 403 recycling, 360 trihalides, 358, 374 aluminophosphate, 686, 688 aluminosilicate, 360, 446 aluminosilicates, 385, 401 aluminosilicates as acid–base catalysts, 150 alums, 358 Alzheimer’s disease, 741 ambidentate, 210, 466 americium, 649 amethyst, 382 amine oxidases, 796 amino acids (table), 768 aminoborane, 366 ammonia, 320, 410, 412, 417, 679 biosynthesis, 808 ammonia borane, 356, 360, 365 ammonium carbamate, 395 ammonium chloride, 82 ammonium nitrate, 417 ammonium perchlorate, 417 ammonium salts, 417 ammoxidation, 754 amorphous selenium, 441 amosite, 397 amphoteric, 130, 349, 355, 358 amphoterism, 130 anaesthetic, 481 anatase, 236 Ångström, 235 angular nodes, 12, 13 anhydrous oxides, 129 anhydrous sulphuric: solvent, 147 anion conduction, 663 anode, 157 antibonding orbital, 44 antiferromagnetic, 545 antifluorite, 84, 445 antimalarial drugs, 826 antimonides, 417 antimony, 408 antimonides, 410 halides, 410, 419 organometallic compounds, 428 oxide, 411 oxides and oxoanions, 425 pentafluoride, 135 stibane, 410, 419 uses, 414 apatite, 689 apoprotein, 769 apoptosis, 439 applications of vibrational spectroscopy, 246 APS, see adenosine pyrophosphate aqua acid, 125 aqua acid strengths (periodic trends), 127 aqua regia, 423 arachno-boranes, 369 aragonite, 347 arene ligand, 593 argentite, 508 argon, 479 compounds, 486 coordination compounds, 485 uses, 481 aromatic hydroxylation, 754 arsabenzene, 429 arsane, 419, see also arsine arsenic, 408 allotropes, 409 arsane, 419 arsenides, 410 arsine, 410 extraction, 412 halides, 410, 419 in the environment, 412 organometallic compounds, 428 oxide, 411, 414 oxides and oxoanions, 425 uses, 414 arsenic trioxide: in leukemia treatment, 824 arsenicals, 414 arsenides, 376, 417 arsenite oxidase, 427 arsenoamide, 414 arsenolite, 410, 414 arsenopyrite, 410 arsine, 410 arsole, 430 arsonium ion, 419 arthritis treatment, 824 artificially layered materials, 717 arylarsanes, 429 asbestos, 382, 397 asbestosis, 397 associative rate determining step, 554 associative mechanism, 553 astatine, 456 atactic, 757 atmophile, 279 atmosphere, 435 atom economy, 732 atomic absorption spectroscopy, 260 atomic force microscopy, 266 atomic layer deposition, 712 atomic number, atomic orbital, atomic radii, 22, 75, 273, 274 atomization, enthalpy of, 278 ATP, see adenosine triphosphate Aufbau principle, 17 Auranofin®: treatment of arthritis, 824 austenite, 77 autoionization, 119 autoprotolysis, 119 axis: principal, 189 of rotation, 189 azides, 410, 415 azimuthal quantum number, background radiation, 480, 481 Bailar twist, 567 864 Index balancing redox reaction equations, 156 Balmer series, band gap, 383, 698 bands, 107 Banks, R.L., 756 barite, 434 barium, 336 Bartlett, Neil, 482 barycentre, 516 base hydrolysis, 565 bases, 116 basic solvents, 145 ‘basket’ porphyryin, 782 BaSO4, 101 BaTiO3, 670 batteries: metal hydride, 312 bauxite, 355, 360 Beer–Lambert law, 241 benzene ligand, 593 Berry pseudorotation, 220, 567 beryl, 340, 396 beryllium, 336, 339 methide, 400 beryllocene, 351 bicarbonate, 329, 394 bidentate, 210 Big Bang, BIMEVOX, 664 BINAP, 736 binary carbides, 385 binding energy, bioconjugation: conferring selectivity on metal-containing drugs, 823 biodegradeable polymers, 428 biogenic, 438 bioinformatics, 772 bioinspired catalysis, 817 biological hydrogen cycle, 297 biological metal-coordination sites, 767 biological uses of the elements, 815 biomass, 394 biomineral, 689, 813 biomineralization, 814 biphasic catalysts, 760 bis(triphenylphosphine)iminium cation, 428 BISCO, 509 bismabenzene, 430 bismite, 412 bismuth, 408, 673 citrate, 825 extraction, 412 halides, 410, 419 in medicine, 414 organometallic compounds, 428 oxide, 411 oxides and oxoanions, 425 subsalicylate, 825 bismuth compounds in treatment of gastric ulcers, 825 bismuthides, 417 bismuthinite, 412 bismuthole, 430 blast furnace, 182 bleach, 365, 443, 451, 462, 471, 475 block-copolymer, 719 Blu-ray, 360 blue copper oxidases, 796 ‘blue’ copper centres, 787 BNCT, see boron neutroncapture therapy body-centred cubic, 74 body-centred unit cell, 67 Bohr radius, 13 Bohr, Niels, bond correlations, 51 bond enthalpy, 51, 58, 60, 286, 384 bond length, 51, 58, 238 bond length error, 238 bond order, 50 bond strength, 58 bond strengths: E–H bonds, 300 bonding orbital, 44 bone, 814 formation, role of zinc enzymes, 790 boranes, 356, 361, 367, 370 borate glass, 365 borax, 359, 364 borazine, 366 boric acid, 359, 361, 363, 364 Born equation (solvation), 124 Born–Haber cycle, 91, 325 Born–Mayer equation, 93, 112 borohydrides, 359, 367, 370 Brønsted acidity, 371 boron, 354 boranes, 356, 367 borate esters, 364 borides, 366 borohydrides, 367 carbide, 400 carboranes, 372 clusters, 359 glasses, 365 halides, 364 hydrides, 361 metallaboranes, 372 nitride, 357, 360, 365, 415, 469 nitrogen compounds, 365 organo compounds, 377 oxide, 357, 359 oxygen compounds, 364 polyborates, 364 tetrafluoridoborate, 363 tetrahydridiborate, 362 trihalides, 134, 357, 363 boron neutron-capture therapy, 368 borosilicate glass, 360, 365, 397, 678 Bosch, Carl, 417 bottom-up synthesis, 707 boundary surface, 13 Brackett series, Bragg’s equation, 235 Brandt, Hennig, 412 brass, 78, 106, 510 bridging ligand, 585 bromates, 475 bromine, 456 bromides, 466 interhalogens, 468 occurrence, 458 oxides, 459, 471 oxoacids and oxoanions, 471 production, 461 trifluoride, 468 uses, 462 bromite ions, 474 bromous acid, 474 Brønsted acid, 117, 125 Brønsted base, 117 Brønsted–Lowry theory, 117 bronze, 383, 491 tungsten, 499 Buckminster Fuller, 385 buckyballs, 382 building-up principle, 17, 46 butadiene ligand, 591 butyllithium, 373 C60, 703 Ca doped ZrO2, 105 cadmium, 510 cadmium chloride, 85 cadmium iodide, 85 cadmium sulfide, 698, 709 caesium, 318 caesium chloride, 82, 320 caesium chloride structure, 325 CaF2, 84 calciferation, 814 calcite, 347 calcium, 336, 770 carbonate, 347 comparison with magnesium in biology, 776 carbonate crystals in the mammalian gravity sensor, 814 hydride, 310 phosphate, 413 signalling proteins, 775 silicate, 412 calmodulin, 775 Calvin cycle, 396 cancer, 821 cancer treatment, 821 caprolactam, 418 carbamate as ligand to magnesium in ‘rubisco’, 791 carbene: complex, 603 Fischer, 597 ligand, 597 N-heterocyclic, 597 Schrock, 597 singlet, 597 triplet, 597 carbenes, 405 carbides, 320, 385, 398 alkali metal, 330 alkaline earth, 346 metallic, 400 metalloid, 400 saline, 399 carbon, 381 amorphous, 389 black, 389, 699 carbonyl halides, 392 cyanide, 384 cyanides, 398 cycle, 394 diamond, 382, 385 fibres, 389 fullerenes, 382, 388 graphene, 382, 386 graphite, 382 halides, 384 hydrocarbons, 390 hydrogencarbonate, 394 nanotubes, 382, 389 oxides, 384 oxo compounds, 394 partially crystalline, 389 sulfur compounds, 394 tetrahalides, 392 carbon dioxide, 384, 394 greenhouse effect, 394 Lewis acid, 133 phase diagram, 149 sequestration, 395 superfluid, 396 carbon monoxide, 384, 394, 585 competition with oxygen for binding at haemoglobin, 783 dehydrogenase, 807 in biology, 806 in medicine, 828 Lewis acid, 137 molecular orbital theory, 49 releasing molecules (CORMs), 828 sensors in biology, 812 carbon nanotubes, 713 carbon suboxide, 384 carbonates, 99 alkali metal, 328 alkaline earth, 346 Index carbonic acid, 394, 396 carbonic anhydrase, 394, 789 carbonyl, 585 carbonyl stretching frequencies, 586 Carboplatin®: treatment of cancer, 822 carboranes, 359, 372 carborundum, 385, 400 carboxylates (amino acids) as ligands, 770 carboxylic acid linkers, 692 carboxypeptidase, 789 Cardiolyte®: used in heart imaging, 832 Cardiolyte®, 502 cassiterite, 382, 386 catalase, 793 catalysis, 385, 728 activity, 731 alkene metathesis, 733 ammonia synthesis, 748 asymmetric oxidations, 739 biphasic, 760 C–C bond-forming reactions, 740 catalytic cracking, 749 electrocatalysis, 752 electrochemical hydrogen production and oxidation, 315 ethanoic acid synthesis, 742 Fischer–Tropsch synthesis, 751 heterogeneous, 732, 742 homogeneous, 732 hydroformylation, 736 hydrogenation of alkenes, 734, 747, 759 inspiration from metalloenzymes, 817 multiphasic, 743 oligomerization and polymerization, 755 partial oxidation of hydrocarbons, 754 photocatalysis, 752 poison, 729 regeneration, 731 selectivity, 731 sulfur dioxide oxidation, 749 support, 743 Wacker oxidation of alkenes, 738 catalytic converters, 745 catalytic cycle, 730 catenand, 231 catenane, 230 catenation, 383, 390, 434, 440 cathode, 157 cation conduction, 661 cation conductivity, 679 cationic interhalogens, 468 Cativa process, 742 CdCl2, 85 CdI2, 85 CdSe nanocrystals, 722 CdTe, 702 cell membrane, 763 cells: structure and organization, 763 cement, 137, 341 cementite, 400 Ceretec®: used in brain imaging, 832 cerium oxide, 636 cerium tetrafluoride, 637 CFCs, see chlorofluorocarbons chalcogens, 433 chalcophile, 279 character, 193 character table, 193 charge-transfer reaction, 574 charge-transfer transition (Lewis adduct), 136 chelate: complex, 212 effect, 212, 229, 364 chelating ligand, 212 chelation therapy, 828 chemical analysis, 260 chemical beam epitaxy, 712 chemical shift, 248 chemical vapour deposition, 712 chemiosmotic theory, 784 chemisorption, 746 chemolithotropy, 394 Chevrel phase, 684 china clay, 401 chiral, 220 chiral molecule, 196 chiral resolution, 223 chirality, 196, 222 chloralkali industry/process, 323, 461 chlorate, 459 chloride, 681 ionic, 290 chlorine, 456 chlorides, 466 dioxide, 470, 475 interhalogens, 468 occurrence, 458 oxides, 459, 470 oxoacids and oxoanions, 471 production, 461 uses, 462 chlorine-based bleach, 475 chlorite ions, 474 chlorodifluoromethane, 476 chlorofluorocarbons, 395, 458, 462, 475 chloroform synthesis, 462 chlorophyll, 350, 413 chloroplast, 764, 800 chlorous acid, 472, 474 CHN analysis, 260 chromium, 498 chrysotile, 397 CIGS, 509 cinnabar, 510 CIS, see copper indium diselenide cisplatin, 821, 822 cis–trans isomerism, 219, 221 class, 194 clathrate hydrates, 309 clathrates, 391, 480, 486 Claus process (production of sulfur), 183, 440 clays, 355, 360, 382, 385, 401, 689, 750 Clebsch–Gordan series, 531 clinical trials, 821 close packing, 69, 89 close-packed structures, 74 closo-boranes, 369 cluster, metal, 218, 610 cluster valence electrons, 611 CMR, see colossal magnetoresistance Cn, 189 CNTs, see carbon nanotubes cobalamin, 506, 802 cobalt, 506 enzymes in radical-based rearrangement reactions, 803 enzymes, 802 methionine synthase, 803 cobalt–carbon bond, 802 coenzyme B12, 802 coinage metals, 292 colossal magnetoresistance, 503, 674 colour, 242 colour wheel, 242 compartmentalization, 766 complex, 209 16-electron, 581 18-electron, 581 formation, 138, 141 high-spin, 518 homoleptic, 599 inner-sphere, 210 low-spin, 518 octahedral, 216, 221, 516 outer-sphere, 210 polymetallic, 218 spin crossover, 546 square-planar, 215, 219, 523 square-pyramidal, 220 tetrahedral, 215, 220, 522 trigonal-bipyramidal, 220 trigonal-prismatic, 216 complex (adduct) formation, 139 complex chloride, 681 complex hydrides, 694 complex nitride, 679 865 complex oxide, 667 complexation: influence on reduction potential, 168 comproportionation, 167 computational methods, 56 concentrated sulfuric acid, 437 concrete, 341 condensation, 131 condensed phosphates, 427 conductivity, 107 conjugate acid, 117 conjugate base, 117 constructive interference, contact process, 451 contraction: lanthanoid, 24 coordination compound, 209 alkali metal, 332 coordination: isomerism, 218 number, 86, 210, 285 sphere, primary, 210 copper, 508 complexes in radiotherapy, 824 coordination, 672 in biological electron transfer, 787 in oxygenases, 799 in reversible oxygen binding, 781 linear coordination, 813 sensing proteins, 813 copper indium diselenide, 703 copper semithiocarbazone complexes in radiotherapy, 824 copper-sulfur cluster in nitrous oxide reductase, 809 core–sheath nanowires, 715 core–shell nanoparticles, 710 corrin as ligand, 771 corundum, 360, 376, 667 Cossee–Arlman mechanism, 755 counting electrons, 582 coupling, 249 coupling reactions, 740 covalent: halide, 290 nitrides, 410 radius, 23, 58 critical temperature, 671 crocidolite, 397 crown ethers, 332 cryolite, 360, 375, 467 cryptand, 377 crystal structure, 66 crystal system, 66 crystal-field splitting parameter, 516 crystal-field theory, 515 866 Index crytands, 332 CsCl, 82, 320 cumene process, 754 Curie temperature, 545 curing meat, 424 Curl, Robert, 385 CVE, see cluster valence electrons cyanide, 384, 398 cyanogen, 384, 398, 415, 465 cyclams as anti-HIV agents, 827 cyclic voltammetry, 264 cyclobutadiene, 591 cycloheptatriene, 595 cyclopentadiene, 595 cysteine, 435, 443 ligand, 770 cytochrome c, 784 complex with other proteins, 785 oxidase, 398, 794 oxidase analogue, 795 oxidase mechanism, 795 peroxidase, 793 cytochrome P450: mechanism, 797 cytochromes, 784 cytoplasm, 764 cytotoxicity, 820 Czochralski process (production of silicon), 182 d orbital, 11 data storage, 674, 675 d-block metal, 488 DCD, see Dewar–Chatt– Duncanson d-d reaction, 574 d-d transitions, 536 de Broglie, Louis, decaffeination, 396 decamethycyclopentasiloxane, 404 defects, 102, 659 Deferiprone®: treatment of iron overload, 828 deferrioxamine, 828 degeneracy, 195 degenerate orbital, 53 delayed reaction, 574 density, 73, 319, 337 density functional theory, 57 density of states, 109 dental health, 462 Desferasirox®: treatment of iron overload, 828 Desferral®: treatment of iron overload, 828 deshielded, 249 desorption, 746 destructive interference, detergents, 427 deuteration, 246 deuterium, 4, 297 Dewar–Chatt–Duncanson, 590 diagonal relationship, 293, 355 diamagnetic, 520 diamond, 382, 385 diars ligand, 429 diborane, 306, 356, 361, 368 molecular orbital theory, 56 dibrominium ion, 468 dicarbides, 399 dichloromethane synthesis, 462 dielectric constant See relative permittivity Diels–Alder reaction, 439 differential scanning calorimetry, 263 differential thermal analysis, 263 diffraction, 234 pattern, 236 diffractometer, 237 diffusion, 660 dihydrogen ligand, 589 dihydrogen complexes, 313 diiodinium ion, 468 diiodocarborane, 373 dilithiocarboranes, 373 dimethylsulfane, 375 dinitrogen ligand, 598 dinitrogen oxide, 411, 416, 425 dinitrogen pentoxide, 423 dinitrogen tetroxide, 411, 423 as a solvent, 148 dinitrogen trioxide, 411, 424 diodes, 360, 376, 377, 401, 414, 447 dioxygen, 438, See oxygen dioxygen difluoride, 470 dioxygenases, 796 dioxygenases: mechanism, 798 DiPAMP, 736 disilicate, 384, 396 dispersion forces, 95 displacement reactions, 138 disproportionation, 167, 172, 422, 472 dissociation: constant, 227 energy, 45 dissociative rate determining step, 554 dissociative mechanism, 553 distortion: rhombic, 216 tetragonal, 216, 524 disulfide, 445, 682 disulfite, 449 disulfur dichloride, 445 disulfurdinitride, 415, 437, 453 disulfurous acid, 451 dithionate, 437, 449 dithionic acid, 452 dithionite, 449 dithionous acid, 452 dolomite, 340 domain, 670 donor-pair: counting electrons, 582, 584 dopant, 105 doping, 701 Doppler effect, 254 double exchange, 674 Drago–Wayland equation, 142 drug delivery, 428 drug development, 821 drug discovery, 821 drug target, 821 DSC, see differential scanning calorimetry DTA, see differential thermal analysis Du Pont method, 386 dynamic Jahn–Teller effect, 524 EAN rule, 581 Earth’s core, 75 EDAX, see energy dispersive analysis of X-rays EDS, 262 effective atomic number rule, 581 effective nuclear charge, 15, 27 Egyptian blue, 697 Eigen–Wilkins mechanism, 560 electric field gradient, 254 electrical insulator, 365 electrocatalysis, 752 electrochemical: extraction of elements, 183 insertion, 683 series, 161 techniques, 264 water splitting, 438 electrochromic, 678 electromagnetic: force, spectrum, 7, 240 electron: affinity, 28 counting in clusters, 611 deficiency, 56, 356, 358 deficient hydrogen compounds, 306 impact ionization, 258 microscopy, 267, 660 paramagnetic resonance, 252 self-exchange reaction, 570 spin resonance, 252 transfer in biology, 783 electron-gain enthalpy, 28 electron-transfer relays in enzymes, 786 electronegativity, 29, 59, 277 Allred and Rochow, 30 Ketelaar triangle, 60 Mulliken, 30 Pauling, 59 electronic conduction, 666 electronic structure, 107 electrostatic: parameter, 98, 124 potential surface, 57 elements in biology, 764 Ellingham diagram, 179 emerald, 104, 397 emery, 360 emission spectroscopy, 239, 242 enantiomer, 197, 223 enantiomeric excess, 736 enantiomeric pair, 220 enantioselective reactions, 735 encounter complex, 571 encounter pair, 560 endohedral fullerene complexes, 486 energy dispersive analysis of X-rays, 262 entering group, 550 enterobactin, 778 enthalpy: of atomization, 278 of hydration, 124 entropy of activation, 559 environmental chemistry: use of electrochemical data, 177 enzymes, 413 EPR, see electron paramagnetic resonance as technique for investigating metal sites in proteins, 772 detectability, 253 spectrometer, 253 spectrum of Pu3+, 647 Epsom salts, 434 Ertl, G, 749 ESR, see electron spin resonance eta, 585 ethanoic acid synthesis, 742 ethylene oxide, see oxirane eutrophication, 427 Evans method, 264 EXAFS, 257 technique for investigating metal sites in proteins, 772 exchange energy, 18 exclusion principle, 15 exclusion rule, 198 expanded metal, 331 extended defects, 659 extinction coefficient, 241 extraction of elements using chemical oxidizing agents, 182 Index extraction of elements using chemical reducing agents, 178 extrinsic defects, 103 f orbitals: radial distribution functions, 626 fac, 221 face-centred cubic, 70 face-centred unit cell, 67 Fajan’s rules, 31 f-block elements, 625 Fe1−xO, 665 FeCr, 79 feldspar, 382, 401 Fenton reaction, 442 Fermi level, 109 ferrichrome, 778 ferrihydrite, 779 ferrimagnet, 545 ferritin, 779 ferrocene, 505, 579 compounds in glucose sensors for diabetes patients, 829 Ferrocifen®, 824 ferroelectric, 670 ferromagnet, 545 ferroquine: an anti-malarial drug, 827 ferroxidase centres, 780 fertilizers, 411, 413, 417, 426, 450 fingerprint detection, 454 fireworks, 341 Fischer, 606 Fischer carbene, 597 Fischer–Tropsch synthesis, 387, 751 flame pyrolysis, 710 flame tests, 319, 337 flexible electronic display, 716 fluorapatite, 411 fluorescence, 243, 544 of lanthanoid compounds, 634 spectroscopy, 242 fluoridation, 462 fluorine, 456 fluorides, 466, 680 interhalogens, 468 occurrence, 458 oxides, 470 production, 461 uses, 462 fluorite, 81, 84, 338, 673 fluorocarbons, 458, 475 fluorophile, 382 fluorosis, 462 fluorosulfuric acid, 453 fluxes, 657 fluxional metallocenes, 608 fluxionality, 240, 251 food additives, 426, 427 forbidden transition, 542 formation constant, 226 overall, 227 stepwise, 226 fossil fuel, 395 fossils, 814 fractional atomic coordinates, 68 framework structures, 658, 685 francium, 318 Franck–Condon principle, 543, 539, 571 Frasch process, 440 Frenkel defect, 102 Friedel–Crafts reaction, 137, 372, 375 frontier orbitals, 29 Frost (oxidation state) diagram, 173, 421, 426, 472 frustrated Lewis pair, 141 FTIR spectroscopy, 246 fuel cell, 158, 356, 442 fullerene complexes, 388 fullerenes, 382, 388 endohedral, 389 fullerides, 388, 703 fuming sulfuric acid, see oleum fundamental stretching, 244 fungicides, 405 Fuoss–Eigen equation, 561 furnace, 657 g-value, 252 GaAs, 702 gadolinite, 502 gadolinium bioconjugate MRI tracer for blood clots, 831 gadolinium compounds in magnetic resonance imaging, 830 galena, 382, 434 gallia, 376 gallium, 354 arsenide, 360, 377, 417, 702 hydrides, 374 monohaliodes, 375 organometallic, 378 oxide, 358, 360 oxo compounds, 376 sulfide, 376 trihalides, 358, 374 galvanic cell, 157 GaN, 702 garnet, 639 gas adsorption, 693 gas separation, 687 Geim, Andre, 387 gemstones, 104 geometric isomerism, 219 germane, 392 preparation, 362 germanite, 382 germanium, 381 halides, 384 hydride, 392 organo compounds, 404 oxide, 384 oxides, 397 tetrahalides, 393 germylenes, 404 giant magnetoresistance, 674 Gibbs energy: of activation, 729 of solvation, 124 glass, 383, 384, 397, 441, 676 borosilicate, 397 glass modifier cations, 678 glass transition temperature, 677 GMR, see giant magnetoresistance goitre, 463 gold, 508 complexes as drugs for rheumatoid arthritis, 824 nanoparticles, 708 Goldschmidt classification, 279 Gouy balance, 264 graphene, 382, 386, 387, 389, 715 oxide, 384 graphite, 331, 365, 382, 385, 387, 676 bisulfates, 387 fluoride, 387 intercalation compounds, 399 Grätzel cell, 698, 709 greenhouse effect, 394 greenhouse gas, 391 grey arsenic, 409 grey selenium, 441 Grignard reagent, 351, 363, 429, 741 ground state, 15 ground term, 533 ground-state configurations, 18 Group 1, 318 Group 2, 336 Group 13, 354 hydrides, 374 Lewis acidity, 375 low oxidation state halides, 375 organometallic compounds, 377 oxo compounds, 376 oxo salts, 358 sulfides, 376 trihalides, 358, 374 with Group 15, 376 Zintl phases, 377 Group 13/15 semiconductors, 417 867 Group 14, 381 halides, 384 hydrides, 383, 390 nitrogen compounds, 398 organo compounds, 404 oxides, 384, 394 Group 15, 408, 410 allotropes, 409 antimonides, 410 arsenides, 410 halides, 410 hydrides, 410, 417 nitrides, 410 organometallic compounds, 428 oxo compounds, 411 oxohalides, 420 pentahalides, 420 phosphides, 410 trihalides, 419 Group 16, 433 halides, 436, 444 hydrides, 441 oxides, 436 polyanions and cations, 452 rings and clusters, 437 Group 17, 456 halides, 466 interhalogens, 460, 467 oxides, 470 oxoacids and oxoanions, 459, 471 polyhalides, 460, 469 pseudohalogens, 465 Group 18, 479 clathrates, 486 compounds, 480 coordination compounds, 485 group theory, 188 Grubbs’ catalyst, 733 gunpowder, 441 Haber process, 412, 417, 421 Haber, Fritz, 417 haematin, 827 haemerythrin, 782 haemocyanin, 781 haemoglobin, 398, 434, 504, 781 importance of degradation for malaria parasite, 826 hafnium, 493 covalent, 290 halide, 289 halides: alkaline earth, 338, 343 Hall–Hérault process (production of aluminium), 183, 360 halocarbons, 384 halogenated polymers, 405 868 Index halogens, see Group 17 halogens as Lewis acids, 136 haloperoxidase, 494 hapticity, 585 hard: acids, 139 bases, 139 disk, 674, 675 ferromagnet, 545 hard-soft classification, 139 hardness: consequences, 141 interpretation, 140 Harold, 385 Hartree–Fock method, 57 HCFCs, see hydrochlorofluorocarbons heats of formation: alkali halides, 325 Heck coupling, 740 hectorite, 689 Heisenberg, Werner, Helicobacter pylori (pathogenic bacteria), 825 helium, 479 demand for, 481 helium-II, 481 occurrence, 480, 481 uses, 481 hematite, 435 heterodiamond, 360 heterogeneous: acid-base reactions, 150 catalysis, 732, 742 heterogenized homogeneous catalysts, 755 heterolytic dissociation, 305 heteronuclear coupling, 250 heteronuclear diatomic molecules, 48 hexafluoridophosphate, 471 high-spin complex, 518 high pressure synthesis, 386 high temperature superconductor, 671 high temperature synthesis, 656 higher oxide, 667 highest occupied molecular orbital, 48, 49 histidine as ligand, 770 HIV: drugs based on inorganic chemistry, 827 Hogan, J.P., 756 hole filling, 81, 85 holes in close-packed structures, 70 holoprotein, 769 HOMO, see highest occupied molecular orbital homogeneous catalysis, 732 homoleptic complex, 599 homolytic dissociation, 305 homonuclear: coupling, 250 diatomic molecules, 43, 45 Hoppe, Rudolf, 482 Hund’s rules, 18, 533 hybrid orbitals, 41, 55 hybridization, 41, 55 hydrate isomerism, 218 hydrazine, 418 hydrazoic acid, 416 hydride, 287 gap, 311 ligand, 588 non-classical, 589 hydrides, 106, 324, 694 alkaline earth, 338, 342 molecular, 306 saline, 310 metallic, 311 hydridic character, 301 hydridicity, 307 scale, 313 hydrido complexes, 313 in enzymes, 810 hydroboration, 362, 377, 391 hydrocarbons, 383, 390 hydrochlorofluorocarbons, 475 hydrofluoric acid, 459 hydrofluorocarbons, 458, 462 hydroformylation, 736 hydrogen, 239, 296 adsorption on platinum, 305 agostic, 597 as a fuel, 299 atom, 297 binary compounds, 299 compounds, methods of synthesis, 315 cyanide, 384, 398 cycle, 810 dissociation energy, 298 from fossil fuels, 303 ions, 297 nuclear properties, 302 production, 303 by electrolysis, 304 from renewable resources, 304 properties and reactions, 298 purifier, 312 radical chain reactions, 306 reactions, 305 selenide, 444 small-scale preparation, 303 storage, 356, 694 storage materials, 311, 342 sulfide, 443 telluride, 444 uses of, 296 hydrogen bond enthalpies (table), 308 hydrogen bonding, 307, 435, 441, 458 in nucleic acids, 309 hydrogen fluoride, 412 as a solvent, 147 autoprotolysis, 466 molecular orbital theory, 49 hydrogen peroxide, 442 destruction by metalloenzymes, 793 hydrogenase mechanism, 810 hydrogenases, 786, 810 hydrogenation of alkenes, 734, 747 hydrogencarbonate, 329, 394 alkaline earth, 346 hydrogenic atoms, hydrogenphosphates, 413 hydrogensulfate, 437 hydrogensulfite, 437, 451 hydrometallurgical extraction, 182 hydrosilylation, 391 hydrothermal, 658 hydroxides: alkali metal, 327 hydroxoacid, 125 hydroxyapatite, 411, in biology, 814 hydroxylamine, 418 hyperfine coupling, 253 hypervalence, 41, 54 hypervalent, 460 hypochlorite ions, 474 hypochlorous acid, 474 hypofluorous acid, 474 hypohalite ions, 474 hypohalous acids, 474 hypophosphite, 425 hypoxia, 823 IC50 number, 821 ice: structure, 308, 442 identity operation, 189 imidazole as ligand, 770 improper rotation, 190 indium, 354 monohalides, 375 organometallic, 378 oxide, 358 oxo compounds, 376 sulfide, 376 trihalides, 358, 374 indium tin oxide, 7, 376 inert, 551 inert gas rule, 580 inert-pair effect, 358, 382, 384, 410 infrared: spectrometer, 245 spectroscopy, 197, 244, 245, 347 inner-sphere mechanism, 568 inorganic: elements in medicine, 820 framework chemistry, 690 nanowires, 713 pharmacology, 820 inorganic–organic nanocomposites, 720 insertion, 619, 682 insulator, 107, 110 intensities in NMR, 250 intercalation, 681, 682 intercalation compound, 155 interchange, 560 interchange mechanism, 553 interference, 44 interhalogens, 460, 467, 483 intermediate, 553 intermetallic compounds, 695 intermetallics, 78, 79, 696 interpseudohalogen compounds, 398 interstitial, 76 interstitial nitrides, 410 intersystem crossing, 544 intrinsic defects, 102 inverse spinel, 668 inversion, 189 centre of, 189 inversion operation, 189 inverted behaviour, 572 iodates, 475 iodic acid, 471 iodine, 456 interhalogens, 468 iodides, 466 occurrence, 458 oxides, 471 oxoacids and oxoanions, 471 polyiodides, 469 uses, 463 ion: diffusion, 660 exchange, 385, 403, 687 mobility, 660 pumps and transporters, 766 transport, 659 ionic: bonding, 66 chloride, 290 conductivity, 660 liquid, 148, 760 model, 126 oxide, 291 radius, 22, 87, 275, 319, 337 solids, 80 ionization: energy, 25, 276 enthalpy, 25, 92 isomerism, 218 potential, 319, 337 ionophores, 773 IR active, 198 IR spectroscopy, 604 iridium, 506 iron, 75, 79, 504 Index iron (IV): importance of in enzyme catalysis, 798 Iron Age, 491 iron: cycle, 777 enzymes catalysing acid-base reactions, 791 in reversible oxygen binding, 781 overload, 828 porphyrin, 398 orbital overlap, 784 proteins as sensors, 811 regulatory protein, 811 transport in organisms, 777 iron-based superconducting materials, 673 iron-carbonyl complexes in enzymes, 810 iron-molybdenum: cofactor, 808 protein, 808 iron-responsive element, 811 iron-sulfur clusters, 785 in acid-base catalysis, 793 in radical SAM enzymes, 804 mixed valence description, 786 irreducible representation, 194 Irving–Williams series, 525, 766 isocyanates, 393 isoelectronic, 50, 361, 365, 376, 398, 403, 416, 424 isolobal, 428, 465, analogies, 612 isomer: optical, 220 shift, 254 isomerism: coordination, 218 geometric, 219 hydrate, 218 ionization, 218 linkage, 218 isomerization, 730 isosbestic point, 242 isotactic, 757 isotopes, 3, 259 isotopologues, 302, 748 ITO, see indium tin oxide Jablonski diagram, 634 jadeite, 397 Jahn–Teller: distortion, 216, 499, 503, 509, 524 effect, 524 jj-coupling, 531 K2NiF4 structure type, 670 K2Pt(CN)4Br0.3·3H2O, 705 Kaminsky catalyst, 756 kaolinite, 385, 401 Kapustinskii equation, 97 KCP, 705 kernite, 359 Ketelaar triangle, 60, 80 kinases, 791 Kohn–Sham, 57 krypton, 479 compounds, 486 coordination compounds, 485 difluoride, 486 Kursk, 443 L type ligand, 582 lactoferrin, 778 lamp black, 382 Landot, H., 472 lanthanoid (II) compounds, 637 lanthanoid compounds: magnetic properties, 634 lanthanoid: contraction, 24, 489 ion luminescence, 633 metals, properties and uses, 627 lanthanoid-based phosphors and lasers, 635 lanthanoids, 488, 625 absorption spectra, 632 atomic properties, 629 atomization energies, 630 binary ionic compounds, 636 coordination compounds of Ln2+ and Ln4+, 640 coordination compounds of Ln3+, 639 electronic and magnetic properties, 632 electronic structures, 629 hydration energies of 3+ ions, 631 ionization energies, 629 ligand-field effects, 630 occurrence and recovery, 627 organometallic compounds, 641 radii, 630 separation by ion exchange, 640 standard potentials, 631 term symbols, 632 ternary and complex oxides, 638 in Zeigler-Natta polymerization and σ-bond metathesis, 642 lanthanum, 491 lanthanum barium copper oxide, 671 Laporte selection rule, 542 Latimer diagram, 171 lattice, 66 enthalpy, 91, 96, 656 parameter, 66 points, 67 laughing gas, 411 laundry powders, 365 Laves phases, 695 layered disulfides, 446 layered double hydroxides, 689 layered sulfides, 681 LCAO approximation, 43 L-dopa, 736 lead, 381 halides, 393 hydride, 384, 392 organometallic compounds, 405 oxide, 384 oxides, 397 lead-acid batteries, 398, 441 leaving group, 550 LED, 701, 722 Lewis acid, 209, 361 Lewis acid (definition), 132 Lewis acidity, 132 Lewis acids and bases (classification), 140 Lewis base, 209, 371 Lewis structures, 34 LFAE, see ligand field activation energy LFER, see linear free energy relation LFSE, see ligand-field stabilization energy Li-ion battery, 676 Li3N, 679 LiCoO2, 675 LiFePO4, 676 ligand, 209 ambidentate, 210 chelating, 212 chirality, 224 field activation energy, 564 macrocyclic, 230 spectator, 563 strong field, 517 substitution, 550 substitution reaction, 614 tripodal, 215 weak field, 517 ligand-field: splitting parameter, 516 stabilization energy, 518, 551, 669 theory, 515, 525 transitions, 536 ligand-to-metal charge-transfer transition, 540 linear free energy relation, 562 linkage isomerism, 218 liquid ammonia, 331, as a solvent, 146 liquid crystals, 706 lithium, 318 battery, 323 869 cobalt oxide, 675 extraction, 322 hydridoaluminates, 695 resources, 322 tetrahydridoaluminate, 374 in treatment of bipolar disorders, 826 lithium ion conduction, 662 lithophile, 279 living cells: inorganic composition (table), 765 LMCT, see ligand-to-metal charge-transfer transition localization, 54 lodestone, 504 Lowenstein’s rule, 686 lowest unoccupied molecular orbital, 48, 49 low-spin complex, 518 lubricant, 682 luminescence, 243, 543 LUMO, see lowest unoccupied molecular orbital Lyman series, macrocyclic: effect, 229 ligands in biology, 771 Maddrell’s salt, 427 Madelung constant, 94 magic angle spinning NMR, 251 magnesium, 99, 336 ATP complex, 767 diboride, 367 enzymes, 791 hydride, 310 magnetic: diffraction, 239 quantum number, 9, 10 resonance imaging: use of Xe, 482 susceptibility, 264, 544 magnetism, 666 magnetite, 435 as direction sensor in bacteria, 814 magnetogyric ratio, 247 magnetometry, 264 magnetotactic bacteria, 814 malaria, 826 MALDI, 258 manganese, 502 Frost diagram, 176 in photosynthetic oxygen production, 801 manganites, 674 many-electron atoms, 4, 15 MAO, see methyaluminiumoxane marcasite, 446 Marcus cross-relation, 573 Marcus equation, 571 870 Index mass number, mass spectrometry, 257 materials chemistry, 655 materials synthesis, 656 matrix isolation, 484 MBE, see molecular beam epitaxy MCM-41, 719 Meissner effect, 671 Mendeleev, Dmitri, 20 mer, 221 mercury, 74, 510 meridional, 221 mesoporous materials, 718 catalysis, 743 mesothelioma, 397 metal, 20, 65, 107, 109, 280 borides, 366 clusters, 610 disulfide, 682 hydrides, 694 oxides, 445, 665 structures, 72, 73 sulfides, 445 metal-ion activated proteins, 769 metallaboranes, 359, 372 metallic: bonding, 65 carbides, 385, 400 hydrides, 300 nanoparticles, 723 radius, 23, 76, 319, 337 metallocene, 606 fluxionality, 608 metalloenzymes, 440 metalloid, 381, 385, 434 metalloid carbides, 400 metalloids, 20 metallomic investigations flow chart, 765 metallomics, 764, 820 metalloneurochemistry, 817 metalloproteins, 767 metal–metal bond, 499, 610 metal–organic chemical vapour deposition, 712 metal–organic frameworks, 691 metal-to-ligand charge-transfer transition, 540 metasilicate, 396 metastable, metastasis (in cancer), 823 metathesis, 139, 361, 430, 733 methane, 390 clathrates, 391 methane monoxygenare, 798 methanesulfonic acid, 466 methanides, 399 methanol carbonylation, 742 methides, 399 methionine, 443 as ligand, 770 methyaluminiumoxane, 756 methyl transfer reactions in enzymes, 803 methylberyllium, 350 methylchlorosilanes, 404 methyllithium, 333 Meyer, Lothar, 20 MgH2, 694 mica, 385 micas, 382, 401 microporous: silica, 686 solids, 402 microscopy, 266, 712 microstates, 531 migration, 619 migratory insertion reaction, 619 Minamata, 511 mirror plane, 189 dihedral, 189 horizontal, 189 vertical, 189 mischmetal, 492 mitochondria, 764 mitochondrial respiratory chain, 783 mixed ionic-electronic conductors, 664 MLCT, see metal-to-ligand charge-transfer transition MO, 665 MO theory, 43 MOCVD, see metal–organic chemical vapour deposition MOFs, see metal–organic frameworks molar absorption coefficient, 241 molecular: beam epitaxy, 711 geometry, 246 magnets, 705 mechanics, 56 orbital, 203 separation, 687 sieves, 385, 402, 687 term symbols, 536 vibrations, 244 molecular orbital theory, 42, 369 ammonia, 53 antibonding orbital, 44 bonding orbital, 44 carbon monoxide, 49 diborane, 55 electron deficiency, 55 heteronuclear diatomic molecules, 48 highest occupied, HOMO, 48 homonuclear diatomic molecules, 45 hybridization, 55 hydrogen fluoride, 49 hypervalence, 54 LCAO, 43 lowest unoccupied, LUMO, 48 phosphorous pentachloride, 55 polyatomic molecules, 52 sulfur hexafluoride, 54 water, 55 Møller–Plesset perturbation theory, 57 molybdenum, 498 enzymes, 805 molybdopterin, 771 Mond, Ludwig, 579 Mond process, 507, 600, 747 monodentate, 210 monooxygenases, 796 monophosphides, 416 monosulfides, 445 Monsanto process, 742 Montreal protocol, 463 Mössbauer spectroscopy, 254 MS2, 682 mu, 585 Mulliken electronegativity, 30 Mulliken, Robert, 29 multi-walled nanotubes, 389 muscovite, 385 Myochrisin®: treatment of arthritis, 824 myoglobin, 424, 780 N-heterocyclic carbene, 597, 734 NaCl, 320 nanomaterials, 707 nanoparticle, 243 nanosized reaction vessels, 711 nanotubes, 382, 389 NASICON, 661 Nd:YAG, 492 Néel temperature, 545, 667 negative catalyst, 729 neodymium in laser materials, 638 neon, 479 nephelauxetic, 539 neptunium, 649 Nernst equation, 162 neutral-ligand: counting electrons, 582 neutron diffraction, 238 n-fold rotation, 189 n-fold rotation axis, 189 NHC, see N-heterocyclic carbene NHC ligand, 510 NiAs, 84 nickel: arsenide, 84 in hydrogenases, 810 in carbon monoxide dehydrogenase, 807 nido-boranes, 369 NiO, 666 nitrate ion, 411 nitrate reductase, 809 nitric acid, 411, 421, 447 nitric oxide, see nitrogen oxide nitric oxide sensors in biology, 812 nitric oxide synthase, 809 nitride, 330, 410, 415, 679 alkaline earth, 346 covalent, 415 interstitial, 415 saline, 415 nitrido ligand, 416 nitrites, 329 nitrogen, 408 activation, 414, 808, 809 ammonia, 410 cycle, 413, 807 dioxide, see nitrogen oxide Frost diagram, 174 halides, 410, 419 hydrides, 417 monoxide ligand, 598 nitrides, 410, 415 nitrosyl halides, 420 nitryl halides, 420 oxides and oxoanions, 411, 421, 424 production, 412 tribromide, 419 trichloride, 419 trifluoride, 419 triiodide, 419, 469 nitrogen(II) oxide, 411, 424 biological role, 411 nitrogen(IV) oxide, 411, 423, 424 nitrogenase, 415, 498, 808 nitronium ion, 450 nitrosonium ion, 424 nitrous acid, 411, 424 nitrous oxide reductase, 809 NMR, see nuclear magnetic resonance noble character, 292 noble gas ligand, 597 noble gases, see Group 18 nodal plane, 13 nodes, 11 angular, 12, 13 radial, 11 non-aqueous solvents, 142 nonlabile, 551 nonmetals, 20 nonstoichiometry, 102, 105 normal mode, 244 normal modes, 198 normal spinel, 668 Novoselov, Konstantin, 387 nuclear: charge, effective, 15 Index fission, 5, 644 fusion, 5, 302 magnetic resonance, 247, 249, 264, 604 reactors, 481 spin, 247 spin characteristics, 248 nucleon number, nucleophilic: discrimination factor, 557 substitution, 552 nucleophilicity, 552 parameter, 556 nucleosynthesis, nucleus (cell), 764 occupied space, 70 octahedral complex, 221, 516 octahedral hole, 89 octahedral holes, 71 octet rule, 34 octet expansion, 41, 54 oleum, 136, 436, 451 oligomerization, 756 one-dimensional metals, 704 one-equivalent process, 569 opal, 382 optical isomer, 220, 222 optical properties, 697 optically active, 197 orbital angular momentum quantum number, orbital approximation, 15 orbital, molecular, 203 orbital overlap, 108 order of a group, 195 organelles, 764 organoaluminium, 377 organoarsanes, 419 organoarsenic, 428 organoboranes, 485 organoboron, 377 organogermanium, 404 organolithium, 333, 429 organometallic compounds: alkali metals, 333 alkaline earth, 350 lanthanoids, 641 organometallic drugs in treatment of malaria, 826 organophosphines, 419 organosilicon, 404 organoxenon, 484 Orgel diagram, 537 orpiment, 410 ORTEP, 238 orthoclase, 402 orthorhombic sulfur, 440 orthosilicate, 384, 396 oscillating reactions, 472 osmium, 504 osteoblasts, 428 Ostwald process, 412, 421 Ostwald ripening, 708 outer-sphere mechanism, 568 overpotential, 184 oxalate ion, 424 Oxaliplatin®: treatment of cancer, 822 oxidases, 794 oxidation, 154 number, 61, 171 state, 61, 100, 281 oxidative addition, 392, 589, 617, 742 oxide, 291, 320, 445 alkali metals, 326 alkaline earth, 344 ion conductor, 663 nanoparticles, 709 nitride, 680 oxidizing agent, 154 oxirane, 438 oxoacid, 125, 127 oxochlorides, 420 oxofluorides, 420 oxophile, 382 oxygen, 256, 433 abundance, 434 allotropes, 438 atmosphere, 435 atom transfer, energetics, 806 atom transfer by enzymes, 805 binding (reversible) by small molecules, 782 binding to myoglobin, 780 difluoride, 444, 459, 470 evolving centre of photosynthesis, 801 extraction, 438 halides, 444 as an oxidizing agent, 167 singlet, 439 sensing in higher organisms, prolyl oxygenases, 812 transport in living organisms, 780 triplet, 438 oxygenases, 796 oxygen-evolving centre, 801 oxygen-sensing by iron proteins, 812 ozone, 434, 438, 439, 447, 462 hole, 462 ozonide, 439 p orbital, 11 pairing energy, 518 palladium: propensity to adsorb hydrogen, 311 paramagnetic, 520 Paris green, 414 Parkinson’s disease, 741 Paschen series, Pauli exclusion principle, 15, 44, 45 Pauling electronegativity, 59 Pauling’s rules, 128, 459, 471 Pauson–Khand reaction, 751 pearlescent pigments, 699 Pechini, 657 Peierls’ theorem, 705 penetration, 15, 16 pentaiodide ion, 469 pentaphenylarsenic, 430 pentathionate, 437 peptide bond, 767 Pepto-Bismol®: in treatment of H pylori infections, 825 perbromate, 471, 475 perchlorate, 471 perchlorates, 473 perchloric acid, 471 periodate, 471, 473 periodic acid, 471 periodic table, 20, 273 block, 21 period, 21 periplasm, 764 perovskite, 81, 86, 658, 669, 674, 718 structure, 467, 638 peroxidase, 793 peroxide, 326, 344, 445 peroxisome, 764 peroxodisulfate, 450 peroxosulfuric acids, 451 perxenate ion, 483 PES, see photoelectron spectroscopy petroleum, 750 pH, 118 distribution diagram, 122 influence on reduction potentials, 164 phase transition, 236, 325 Philips catalyst, 756 phosgene, 393 phosphane, see phosphine phosphate, 425, 688 in biology, 767 phosphazenes, 428 phosphides, 376, 416 phosphine, 410, 419 ligand, 587 phosphite, 425 phospholipid bilayer, 764 phosphonic acid, 425 phosphonium ion, 419 phosphorescence, 544 phosphoric acid, 425, 427 phosphors, 697 phosphorus, 408 allotropes, 409 halides, 410, 419 nitride, 415 871 oxides and oxoanions, 411, 425 pentachloride, 420 trifluoride, 419 phosphoryl halides, 420 polyphosphates, 427 production, 412 uses, 413 phosphorus(III) oxide, 425 phosphorus(V) oxide, 425 photocatalysis, 699, 752 photochemical reaction, 574 photochromic, 679 photoconductivity, 441 photodynamic therapy, 439 photoelectron spectroscopy, 255 photosynthesis, 394, 434, 800 electron transfer chain, 800 oxygen production, 800 oxygen production, the S-cycle, 801 phototherapy, 823 phthalocyanine, 404 physical vapour deposition, 711 Pidgeon process (extraction of magnesium), 179 piezoelectric, 670 piezoresistance, 386 pigment, 680, 697 pillared clays, 689 pK, 120 plasma synthesis, 710 plastocyanin, 787 platinum, 507 platinum black, 753 platinum drugs in cancer treatment, 821 platinum metals, 292 PLD, see pulsed-laser deposition plumbane, 384, 392 plutonium, 649 as an environmental hazard, 650 valence orbitals, 626 chelation therapy, 828 p-n junctions, 701 pnictogens, 408 point group, 190 point-group symmetry, 189 polar molecule, 196 polarization, 95 polarizability, 31 polonium, 433 polonides, 445, 447 dioxide, 448 polyarsane compounds, 429 polyatomic molecules, 52 polydentate, 210 polyhalides, 460, 469 polyhalogen cations, 468 polyiodide ions, 457 polyiodides, 469 872 Index polymer nanocomposites, 720 polymethylarsane, 429 polymorphism, 74, 236, 347, 384 polynitrogen, 416 polyoxo compound formation, 130 polyoxoanion, 131 polyoxometallate, 132, 495 polyphosphates, 131, 427 polyphosphazene, 428 polyprotic acids, 120 polyselenides, 437, 452 polysulfides, 437, 445, 452 polytellurides, 437, 452 polytetrafluoroethene, 392, 458, 464, 476 polythiazyl, 454 polythionic acids, 437, 452 polytypism, 73 poly(vinyl chloride), 405 pores, 687 porosity, 693 porous carbon, 696 porphyrin, 753 as ligand, 771 potassium, 318 channel, 773 channel, mechanism, 774 coordination sites in proteins, 773 nitrate, 441 transport in cells, 773 Pourbaix (E-pH) diagram, 177 powder X-ray diffraction, 235 primitive: cubic, 74 unit cell, 67 principal axis, 189 principal quantum number, probability density, 9, 44 prodrugs, 823 projection, 68 projection operator, 207 promotion of electrons, 41 prompt reaction, 574 Prosulfuron, 741 protein structure representation, 771 protiodide, 513 proton: affinity, 123 coupled electron transfer in proteins, 788 exchange fuel cell, 159 nuclear magnetic resonance, 303 pump, 794 transfer equilibria, 117 proton-gain enthalpy, 123 Prussian blue, 698 Prussian blue analogues, 706 pseudohalide, 398, 465 pseudohalogen, 398, 465 PTFE, see polytetrafluoroethene pulse radiolysis, 283 pulsed-laser deposition, 711 PVC, see poly(vinyl chloride) PVD, see physical vapour deposition pyrites, 446 pyrochlore, 674 pyrolusite, 502 pyrolytic graphite, 386 pyrometallurgy, 180 pyrophosphate, 443 pyrophyllite, 401 quantization, quantum: confinement, 722 dot, 709, 715, 722 mechanics, numbers, well, 716 yield, 574 quartz, 382 quasicrystals, 78 quicklime, 340 quinol, 486 Racah parameters, 535 radial distribution function, 13 radial nodes, 11 radii, ionic, 22 radiopharmaceutical, radiotherapy, 368, 824 radium, 336 radius: atomic, 22 covalent, 23, 58 metallic, 23 ratio, 88, 325 van der Waals, 58 radon, 479 compounds, 486 occurrence, 480 Raman: active, 198 spectrometer, 245 spectroscopy, 197, 244 Raney nickel, 748 Raschig process, 418 rate-determining step, 553 rate law, 552 ratio of holes to spheres, 72 Ray–Dutt twist, 567 reaction: charge transfer, 574 d-d, 574 delayed, 574 electron self-exchange, 570 photochemical, 574 prompt, 574 with water, 319, 337 reactive oxygen species, 812 realgar, 410, 414 rechargeable battery materials, 675 recycling aluminium, 360 red lead, 384, 397 red phosphorus, 409 red selenium, 441 redox condensation, 614 redox: half reaction, 155 reaction, 154, 568 spectrum of life, 783 stability, 164 reduced mass, 244 reducible representation, 200, 205 reducing agent, 154 reduction, 154 formula, 206 potential, 155 reductive elimination, 617 reflection, 189 relative permittivity, 442 relativistic effects, 25 renewable energy, 438 ReO3, 659, 668 reorganization energy, 571 representation, 205 irreducible, 194 reducible, 200, 205 resonance, 35 respiratory chain, 783 rhenium diboride, 360 rhenium trioxide, 668 rhodium, 506 ring opening metathesis polymerization, 734 ring opening metathesis, 734 Rochow process, 404 rocket fuel, 360 rocksalt, 81, 94, 320, 325, 665, 666, 673 ROM, see ring opening metathesis ROMP, see ring opening metathesis polymerization rotation, improper, 190 rubisco (ribulose 1, 5-bisphosphate carboxylase oxygenase), 396, 792 rubidium, 318 ruby, 104, 360, 376, 667 Ruddlesden–Popper phase, 670 Russell–Saunders coupling, 531 Russian doll model, 389 ruthenium, 504 anti-cancer compounds, 823 ruthenocene, 505 rutile, 81, 84, 236, 398, 445 Rydberg constant, Rydberg, Johann, s orbital, 11 Sabatier, Paul, 747 SALC, see symmetry-adapted linear combination saline: carbides, 385, 399 nitrides, 410 samarium iodide, 637 samarium valence orbitals, 626 sand, 382 sapphire, 104, 360, 376 Satraplatin® :treatment of cancer, 822 s-block: compounds, 101 Lewis acids and bases, 134 scanning electron microscopy, 267 scanning probe microscopy, 266 scanning tunnelling microscopy, 267 Schoenflies symbol, 192 Schottky defect, 102 Schrock: carbene, 597 catalyst, 734 Schrödinger equation, 8, 56 Schrödinger, Erwin, secondary structure (proteins), 769 selection rules, 541 selenides, 436, 445, 447 alkali metal, 327 selenium, 433 dioxide, 448 extraction, 441 hydrides, 443 oxides, 448 oxoanions, 450 oxohalides, 448 polyanions, 452 polycations, 453 polymorphs, 441 polyselenides, 437 sulfides, 445 trioxide, 448 selenocysteine, 770 selenous acid, 441 self-cleaning: coating, 754 windows, 700 self-consistent field, 57 SEM, see scanning electron microscopy semi-empirical methods, 56 semi-metal, 20, 386 semiconducting nanoparticles, 709, 721 Index semiconductor, 107, 110, 360, 376, 383, 391, 410, 441, 700 sensors in biology, 811 sequestration, 395, 427 shapes of molecules, 37 Sharpless epoxidation, 739 shear planes, 660 Shell Higher Olefin Process, 755 shells, 10 shielded, 249 shielding, 15, 16 shielding constant, 16 SHOP, see Shell Higher Olefin Process SiC, 83 siderophile, 279 siderophores, 777 Sidgwick, N.V., 580 silanes, 384, 390 silica, 384, 677, 743 glass, 383 gel, 151 in exoskeletons, 814 silicate, 252, 396, 686 glasses, 397 silicides, 401 silicon, 381, 701 in biology, 814 carbide, 385, 400, 401 compounds with metals, 401 dioxide, 677 extended oxo compounds, 401 halides, 384 hydrides, 384, 390 nitride, 384, 398 nitrogen compounds, 398 organo compounds, 404 oxo compounds, 384, 385, 396 tetrahalides, 393 silicone polymers, 404 silver, 508 single crystal X-ray diffraction, 237 single walled nanotubes, 389 single-molecule magnets, 706 single-photon emission computed tomography, 830 singlet: carbene, 597 oxygen, 439 state, 439 single-walled nanotube, 713 site-directed mutagenesis, 772 skutterudite, 685 Slater’s rules, 16 sleeping sickness, 414 Smalley, Richard, 385 smart windows, 716 smelting, 179 Sn, 190 (SN)x, 704 sodalite cage, 402 sodium, 318 ß-alumina, 661 hydridoborate, 360 ion conduction, 662 perborate, 365 phosphate, 413 pump, 774 sulfite, 451 tetrahydridoaluminate, 360 transport in cells, 773 sodium-sulfur battery, 328 SOFC, see solid oxide fuel cells soft ferromagnet, 545 sol-gel, 657 solar cells, 360, 376, 391, 414 solder, 383 Solganol®: treatment of arthritis, 824 solid acids, 150 solid electrolytes, 661 solid oxide fuel cells, 664 solid solution, 105 solid state chemistry, 655 solid state NMR, 251 solid-state superlattices, 717 solubility, 101 of alkali metal salts, 330 product, 170 solvation, 124 solvent of crystallization, 214 solvent levelling, 142 solvent system definition, 144 solvents as acids and bases, 145 Sonogashira coupling, 741 SPECT, see single-photon emission computed tomography spectator ligand, 552, 563 spectrochemical series, 517 spectroscopic terms, 536 sphalerite, 83, 510 spin, 11 correlation, 18 crossover complex, 521, 546 magnetic quantum number, 11 spin-allowed, 542 spinel, 81, 86, 358, 376, 525, 668, 673 spin-forbidden, 542 spin-only magnetism, 520 spin-orbit coupling, 531 spin-spin coupling, 249 spontaneity, 156 square-planar complex, 215, 219, 523, 581 SQUID magnetometer, 264 SRB, see sulfur-reducing bacteria stability, 100 of oxidations states, 100 standard cell potential, 158 standard conditions, 157 standard entropy change from electrochemical data, 163 standard potential, 156, 157, (table), 161 thermodynamic cycle, 160 in biochemistry, 164 stannane, 384, 392 steel, 77, 495, 498, 502, 504 steric factors in Lewis adducts, 141 stibabenzene, 430 stibane, 419, see also stibine stibine, 410 stibnides, 376 stibnite, 410, 412 stibole, 430 Stille coupling, 740 STM, see scanning tunnelling microscopy Stock, Alfred, 366 Stone Age, 491 street lights, strengths of acids and bases, 126 strong force, strong-field: case, 518 ligand, 517 strontium, 336 structure maps, 90 structure prediction, 89 structure type, 81 subatomic particles, suboxides, 327 subshells, 10 sulfate, 437, 449 sulfide, 106, 436, 441, 445, 681 alkaline earth, 345 alkali metal, 327 sulfite, 437, 449 sulfite oxidase, 806 sulfur, 433 allotropes, 434 cycle, 443 dichloride, 445 dioxide, 136, 436, 447 dioxide oxidation, 749 extraction, 440 halides, 444 hexafluoride, 445 hydrides, 443 nitrogen compounds, 453 occurrence, 434 oxides, 447 oxoacids, 449 oxohalides, 447 873 polyanions, 452 polycations, 453 polymorphs, 440 polysulfides, 437 singlet, 441 trioxide, 136, 436, 447 sulfuric acid, 436, 447, 450 autoprotolysis, 450 manufacture, 451 uses, 450 sulfurous acid, 437, 447, 451 sulfur-reducing bacteria, 443 sulfuryl dihalides, 448 superacid, 149, 420, 750 superbase, 149 superconducting elements, 672 superconductivity, 367, 388, 671, 684, 703 supercooling, 677 supercritical, 486 carbon dioxide as a solvent, 149 fluid, 149 superexchange, 545, 667 superhyperfine coupling, 254 superlattices, 718 superoxide, 326, 445 surface acids, 743 surface bases, 743 surface metals, 744 surface migration, 747 Suzuki coupling, 740 SWNT, see single-walled nanotube symmetry: element, 188 operation, 188 species, 194 symmetry-adapted linear combination, 201, 202, 207 syndiotactic, 757 syngas, 752 synthesis of nanomaterials, 708 synthetic diamonds, 386 tacticity, 757 TAED, see tetraacetylethylenediamine talc, 385, 401 tamoxifen, 824 Tanabe–Sugano diagram, 538 Tc-MAG3®: used in kidney imaging, 832 technetium, 6, 502 compounds in imaging, 830 imaging agents, preparation in hospital, 830 teflate, 448 telluric acid, 450 tellurides, 445, 447 alkali metal, 327 tellurite, 448 874 Index tellurium, 433 dioxide, 448 extraction, 441 hydrides, 443 oxides, 448 oxoanions, 450 oxohalides, 448 polyanions, 452 polycations, 453 polytellurides, 437 trioxide, 448 tellurides, 436, 445 TEM, see transmission electron microscopy template effect, 230 term symbol, 532, 536 of lanthanoid cations, 632 terms, spectroscopic, 531 ternary phases, 85 tethered catalysts, 759 tetraacetylethylenediamine, 360 tetraalkylammonium ion, 430 tetraethyl lead, 405 tetrafluorethane, 458 tetrafluoridoborate, 471 tetrafluoroethene, 476 tetrahalomethanes, 392 tetrahedral: complex, 215, 220, 522 hole, 71, 89 oxoanions, 685 tetrahydridoaluminate, 374, 694 tetrahydridoboranates, 356 tetrahydridoborates, 694 tetramethylammonium ion, 469 tetraphenylarsonium ion, 430 tetraphenylborate, 377 tetraphenylphosphonium ion, 430 tetrasulfurtetranitride, 415, 437, 453 tetrathionate, 437, 451 TGA, see thermogravimetric analysis thalassemia, 828 thallium, 354, 673 as a probe for potassium in proteins, 775 monohalide, 358 monohalides, 375 organometallic, 378 oxide, 358 oxo compounds, 376 sulfide, 376 trihalides, 374 thermal: analysis, 262 stability, 98 thermochemical radii, 98 thermodynamic acidity parameters, 141 thermoelectricity, 684 thermogravimetric analysis, 262, 329 thiocyanate, 466 thiometallate, 446 thionyl dihalides, 448 thiosulfate, 449, 450 thiosulfuric acid, 451 thorium, 648 thorocene, 648 thulium diiodide, 640 thyroid, 463 thyroxine, 463 timescales of characterization methods, 240 tin, 381 allotropes, 383 halides, 393 hydride, 392 hydrides, 384 organometallic compounds, 383, 405 oxide, 384 oxides, 397 TiO, 666 titanium, 493 titanium dioxide, 698, 700 photocatalysts, 754 titanosilicates, 690 Tolman cone angle, 563, 615 tooth decay, 462 toothpaste, 365, 426, 462 top-down synthesis, 707 Tourette’s syndrome, 741 trans effect, 557, 615 trans influence, 557 transcription factors, 776 transferrin, 778 transferrin receptor: control of iron uptake, 811 transistors, 383 transition: allowed, 542 charge transfer, 540 CT, see charge transfer forbidden, 542 transition metal, 488 transition metal oxides, 665 transition state effect, 557 transmetallation, 375, 377 transmission electron microscopy, 267 trichloroborazine, 366 tridentate, 210 triethylaluminium, 378 trifluoridomethanesulfonate, 471 trifluoromethanesulfonic acid, 466 triiodide ion, 469 triiodothyroxine, 463 trimethylaluminium, 377 trimethylamine, 447 trimethylplumbane, 392 trioxidochlorate(V), see chlorate triplet carbene, 597 triplet ground state, 438 triplet oxygen, 440 trithio-carbonate, 396 trithionate, 449 tritium, 4, 297 tube furnace, 657 tungsten, 498 tungsten carbide, 77, 400 tungsten in enzymes: formate dehydrogenase, 806 turnover: frequency, 730 number, 731 two-equivalent process, 569 tyrosine as ligand, 770 ullmanite, 410 ultramarine, 446, 698 ultraviolet photoelectron spectroscopy, 256 ultraviolet-visible spctroscopy, 240 uncertainty principle, unit cell, 66 uranium, 648 halides, 648 preprocessing, 466 uranocene, 648 uranocene: molecular orbital diagram, 649 uranyl ion emission spectrum, 647 urease: a nickel enzyme with a role in stomach ulcers, 825 UV-visible spectrometer, 241 valence bond theory, 39 homonuclear diatomic molecules, 40 hydrogen molecule, 39 polyatomic molecules, 40 valence shell, 21 electron pair repulsion, 36 lone pairs, 38 valinomycin, 332, 773 van der Waals, 386 radius, 58 vapour-phase synthesis, 710 Vaska’s complex, 314, 507 verdigris, 508 vermillion, 510 vibrating sample magnetometer, 264 vibrational analogy, 204 vitamin B12, 506, 802 VO2, 704 volcano diagram, 747 volume of activation, 559 VSEPR, see valence shell electron pair repulsion VSM, see vibrating sample magnetometer vulcanization, 441 Wacker process, 440, 738 Wade’s rules, 368 Wade–Mingos–Lauher rules, 611 Wadsley defect, 659 water, 435, 442 as an oxidizing agent, 165 oxidation, 438 as a reducing agent, 166 softener, 324 stability field, 166 stability range, 165 wavefunction, 8, 39, 43 wavenumber, 244 wave–particle duality, weak-field: case, 518 ligand, 517 Werner, Alfred, 209, 515 white phosphorus, 409 Wilkinson, Geoffrey, 606 Wilkinson’s catalyst, 507, 735, 759 WO3, 659 wolframite, 498 wood preservative, 405 wurtzite, 83, 376, 401, 510 X type ligand, 582 XANES, 257 XAS, see X-ray absorption spectra xenodeborylation, 484 xenon, 479 coordination compounds, 485 fluorides, 480, 482 hydrides, 480 insertion compounds, 484 organo compounds, 484 oxides, 480, 483 oxofluorides, 480, 484 uses, 481 X-ray, 234 absorption spectra, 256 diffraction, 88, 234, 677 fluorescence, 262 fluorescence analysis, 261 spectroscopy, 256 XRF, see X-ray fluorescence YAG, see yttrium aluminium garnet YBa2Cu3O7, 656, 671, 712 YBCO, 671 yellow arsenic, 409 YIG, see yttrium iron garnet yttium-doped zirconia, 661, 663 Index yttrium, 491 aluminium garnet, 492, 638 iron garnet, 492, 638 Zachariasen rules, 677 Zeise’s salt, 508, 579, 581 zeolite, 150, 402, 324, 385, 658, 686 catalysis, 743, 749 zeolite-A, 687 zeotypes, 690 Ziegler–Natta catalyst, 378, 755 zinc, 510 blende, 83, 376, 401 carbonyl mechanism in enzymes, 789 coordination in proteins, 789 coordination sites in proteins, 776 enzymes, 788 finger domain, 772, 776 fluorescent ligands for detection in cells, 832 hydroxide mechanism in enzymes, 789 in alcohol dehydrogenase, 790 in alkaline phosphatase, 790 in transcription, 776 sensing proteins, 813 Zintl phase, 79, 331, 377 zirconia, 663 zirconium, 493 ZnS, 83 α-alumina, 358, 376 α-helix, 770 875 α-hydride elimination, 621 β-hydride elimination, 620 β-sheet, 770 γ-alumina, 358 δ-hydride elimination, 621 η, 213, 585 κ, 210, 213 μ, 213, 585 π backbonding, 586 π-acceptor ligand, 529 π-donor ligand, 529 σ-bond metathesis, 619 χ, 193 Useful relations At T  298.15 K, RT  2.4790 kJ mol1 and RT/F  25.693 mV Conversion factors atm  101.325 kPa  760 Torr (exactly) bar  105 Pa eV  1.602 18 1019 J  96.485 kJ mol1  8065.5 cm1 cm1  1.986 1023 J  11.96 J mol1  0.1240 meV cal  4.184 J (exactly) D  3.335 64 1030 C m T  104 G Å  100 pm  1010 m m  mol dm3 General data and fundamental constants Quantity Symbol Value Speed of light c 2.997 925 108 m s1 Elementary charge e 1.602 176 1019 C Faraday’s constant F  NAe 9.648 53 104 C mol1 Boltzmann’s constant k (kB in case of ambiguity) 1.380 65 1023 J K1 8.6173 Gas constant 105 eV K1 8.314 47 J K1 mol1 R  NAk 8.205 74 102 dm3 atm K1 mol1 h 6.626 08 1034 J s <  h/2π 1.054 57 1034 J s Avogadro’s constant NA 6.022 14 1023 mol1 Atomic mass constant mu 1.660 54 1027 kg Mass of electron me 9.109 38 1031 kg 8.854 19 1012 J1 C2 m1 1.112 65 1010 J1 C2 m1 Planck’s constant Vacuum permittivity 4π Bohr magneton µB  e