Guide for Lecturers

1

Guide for Lecturers by Catherine E. Housecroft

to accompany

Inorganic Chemistry, 2nd edition

Catherine E. Housecroft and Alan G. Sharpe

Contents 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

Some basic concepts Nuclear properties An introduction to molecular symmetry Bonding in polyatomic molecules Structures and energetics of metallic and ionic solids Acids, bases and ions in aqueous solution Reduction and oxidation Non-aqueous media Hydrogen Group 1: the alkali metals The group 2 metals The group 13 elements The group 14 elements The group 15 elements The group 16 elements The group 17 elements The group 18 elements Organometallic compounds of s- and p-block elements d-Block chemistry: general considerations d-Block chemistry: coordination complexes d-Block metal chemistry: the first row metals d-Block metal chemistry: the second and third row metals Organometallic compounds of d-block elements The f-block metals: lanthanoids and actinoids d-Block metal complexes: reaction mechanisms Homogeneous and heterogeneous catalysis Some aspects of solid state chemistry The trace metals of life

2 Appendices

X In going from the 1st to 2nd edition of Inorganic Chemistry, the number of character tables included in Appendix 3 has been increased

1 2 3 4 5 6 7 8 9 10 11

Greek letters Abbreviations Character tables Electromagnetic spectrum Naturally occurring isotopes and their abundances Van der Waals, metallic, covalent and ionic radii for the s-, p- and first row d-block elements Pauling electronegativity values (χP) Ionization energies Electron affinities Standard enthalpies of atomization (∆aHo) of the elements at 298 K Selected standard reduction potentials (298 K)

Target audience for Inorganic Chemistry Inorganic Chemistry is aimed at students reading Chemistry either as a single subject or in a combined degree course. The content is appropriate for first or second year undergraduates onwards and for students taking Masters or Doctorate courses. It should also serve as an appropriate reference text for lecturers of general inorganic chemistry courses, and could be used both for general inorganic courses and for courses structured into modules. A basic knowledge of chemical principles is assumed, although Chapter 1 serves as a review base for: • the structure of the atom; • atomic orbitals; • bonding theories in diatomic molecules; • ionization energies; • electron affinities; • electronegativity; • dipole moments and polar/non-polar molecules; • the isoelectronic principle; • the VSEPR model; • geometrical isomerism.

Organization of Inorganic Chemistry Inorganic Chemistry is structured in four sections, although these Sections are not rigorously defined in the textbook: I Basic concepts – Chapter 1 forms a review base for fundamental principles (see above). II Physical inorganic chemistry – Chapters 2-8 cover: • nuclear properties, including an introduction to the routine use of NMR spectroscopy with nuclei having I ≥ 1/2; • an introduction to molecular symmetry, group theory and vibrational modes of simple molecules; • bonding in polyatomic molecules, using VB and MO theories;

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• structures and energetics of metallic and ionic solids, including packing of spheres, basics of band theory and semiconductors, a survey of common structure types, Born-Haber cycles, Born-Landé equation and related formulae, applications of lattice energies, Frenkel and Schottky defects; • acids, bases and ions in aqueous solution, including sparingly soluble salts, common ion effect, stability constants; • reduction and oxidation with detailed discussion of Eo values and thermodynamic relationships, Nernst equation, dependence of E on factors such as pH and complex formation, potential diagrams and Frost-Ebsworth diagrams, Ellingham diagrams; • non-aqueous media including self-ionization, solvent-oriented definitions of acids and bases – non-aqueous media are exemplified by liquid NH3, HF, H2SO4, CF3SO3H, BrF3, N2O4, selected ionic liquids and supercritical fluids. III Chapters 9-24 – Descriptive chemistry of the elements and principles of coordination chemistry. The treatment of the chemistry of inorganic elements is organized in a fairly traditional manner, with chapters covering: • Hydrogen • Group 1: the alkali metals • The group 2 metals • The group 13 elements • The group 14 elements • The group 15 elements • The group 16 elements • The group 17 elements • The group 18 elements • Organometallic compounds of s- and p-block elements • d-Block chemistry: general considerations • d-Block chemistry: coordination complexes • d-Block metal chemistry: the first row metals • d-Block metal chemistry: the second and third row metals • Organometallic compounds of d-block elements • The f-block metals: lanthanoids and actinoids Principles concerning coordination numbers, structural isomerism, stereoisomerism, crystal field theory, MO theory for octahedral complexes, electronic spectra of dblock complexes, magnetic properties of d-block complexes, CFSE and thermodynamic aspects are the themes of Chapters 19 and 20. Organometallic chemistry of the s- and p-block elements is a rapidly growing field of research and with this in mind, Chapter 18 is devoted to this topic. IV Chapters 25-28 consist of four special topics, each designed to form the basis of a teaching module: • d-Block metal complexes: reaction mechanisms; • Homogeneous and heterogeneous catalysis which includes details of selected industrial processes; • Some aspects of solid state chemistry with an emphasis on applications of materials and development of CVD processes; • The trace metals of life which covers metal storage and transport, dealing with O2, biological redox processes, and Nature’s Lewis acid, Zn2+.

4 At the end of the book, there is a series of Appendices which give tables of physical data, abbreviations and character tables. In the problems in the book, students are encouraged to find data in the Appendices to give practice in extracting data from appropriate compilations.

General features of the 2nd edition of Inorganic Chemistry In Inorganic Chemistry, physical inorganic chemistry forms an important basis for discussions, and thermodynamic and kinetic factors are emphasized throughout the text. Early chapters in the book introduce crucial concepts that are reiterated when descriptive chemistry is discussed – “self-study exercises” throughout the book are used to boost students’ confidence in calculations and in applications of theories and concepts. Inorganic Chemistry contains the following pedagogical features: Use of full colour allows us to pay detailed attention to the production of graphics; 3D-structural figures have, wherever possible, been produced using crystallographic coordinates from the Cambridge Data Base or the Protein Data Bank. Fully worked examples of calculations are followed by self-study exercises with answers. Self-study Exercises throughout the book are used both to practise calculations and to put theory into the context of descriptive chemistry. The exercises proved popular in the 1st edition of Inorganic Chemistry and we have therefore introduced many additional exercises in the new edition. An added feature is the use of literature references in place of direct answers (e.g. interpretation of NMR spectra). Boxed material (many with literature sources for further reading) in three categories: • (i) theoretical and chemical background – the aim of adding theoretical background in “Boxes” rather than in the mainstream text has the advantage that the flow of the general text is not disrupted and the topics are easily found by a reader wishing to refresh his or her memory on background theory. Representative topics are Slater’s rules, exchange energies, thermodynamic 6s inert pair effect, relativistic effects, diffraction methods, Raman spectroscopy, photoelectron spectroscopy, radius ratio rules, nomenclature used for chiral compounds, historical overview of Werner’s work, crystallographic disorders. • (ii) applications – many applications of inorganic chemicals in industry and everyday life are described; representative topics are solar panels, gas sensors, fuels, battery development, nerve gases, sacrificial anodes, catalysts, lubricants, fireproofing, and agricultural chemicals. • (iii) resources, environmental and biological – these boxes illustrate world mineral resources and mining statistics for some important elements, and also emphasize the growing trends in recycling of metals such as aluminium, magnesium and tin; increasing awareness of our environment means that it is timely to include discussions (and literature citations for further reading) of, for example, the greenhouse effect, acid rain, volcanic emissions, fuel emissions, desulfurization, and run-off from phosphate fertilizers. Where

5 appropriate, brief discussions about changes in legislation with respect to the use of chemicals have been included and “Green Chemistry” has been highlighted. Biological aspects of inorganic chemicals are illustrated with, among others, HCN in fruit stones and casava. Highlighted definitions and end of chapter checklists. Throughout the book, new chemical terms are defined in highlighted panels. At the end of each chapter, new terms introduced are listed and the reader is encouraged to ensure that he or she knows the meaning of the new terms. Cross referencing. The book has been planned with principles coming before descriptive chemistry, and in descriptive chapters, we have applied principles from earlier chapters wherever appropriate. To help the student tie principles and their applications together, we have used comprehensive cross referencing between sections in different chapters, and a second colour is used to highlight these references in the text making the reference easy to find but at the same time, ensuring that they do not disrupt the text flow. End of chapter reading lists. The further reading that has been suggested covers a range from general text books to research publications. We are aware that library resources vary, and have given as wide a range of suggestions as possible. These have been thoroughly updated on going from the 1st to 2nd edition of the book. End of chapter problems. Up to 30 problems are provided at the end of each chapter. Chapter 1 also contains a set of Mid-chapter Problems aimed at consolidating fundamental principles from the first half of the chapter. Answers to non-descriptive problems are given at the back of the book, and fully worked answers to all problems are provided in the accompanying Solutions Manual (see later). Nomenclature. IUPAC nomenclature has been used most of the time, but trivial names which are in common use (e.g. acetone) and standard ligand abbreviations which stem from non-IUPAC names (e.g. [ox]2–, [acac]–, H4EDTA) have been retained. Alternative names, e.g. for oxoacids, are introduced in Boxed background material. We appreciate the importance of adhering to IUPAC guidelines, but we have remained realistic in the sense that many trivial names will live on and students must be familiar with them.

Using Inorganic Chemistry: interdependence of chapters Chapter 1 can be used either for direct teaching material or simply as a “review source” for more advanced courses. In it, students can find the necessary fundamental material to support general and advanced inorganic chemistry courses, as well as a reading list of general chemistry texts to which to refer for basic groundwork. Of the physical inorganic chemistry chapters, Chapter 2 should be considered to form the basis of a series of lectures early in a course. Although many courses do not include traditional nuclear chemistry, Chapter 2 in Inorganic Chemistry should not be bypassed – the second half of the chapter introduces multinuclear NMR spectroscopy (including I > 1/2 nuclei) and stereochemically non-rigid molecules;

6 the case studies feature simulated NMR spectra using experimental data and introduce satellite peaks with the interpretation of the 19F NMR spectrum of [XeF 5]–. Chapters 3 and 4 together could form a unit for a series of lectures, but should be taken in sequential order. The coverage of group theory in Chapter 3 is purposely kept at a basic, but informative, level. The discussion and illustrations have been significantly modified in going from the 1st to 2nd edition of the text. The chapter considers the numbers of vibrational modes of simple polyatomic molecules, and introduces selection rules for IR spectroscopy. Raman spectroscopy is introduced as “Boxed” material but is not covered in depth. In Chapter 4, the bonding in polyatomic molecules is addressed, first by using a hybridization approach and then by a ligand group orbital (LGO) approach. The level of coverage of MO theory and the use of group theory to determine the number of LGOs and their symmetry labels for orbitals has been expanded in the 2nd edition of Inorganic Chemistry. As well as showing how to construct MO diagrams for simple molecules such as linear and bent XH2, and trigonal planar and trigonal pyramidal XH3, Chapter 4 teaches students how to use MO theory objectively and illustrates how to deal with partial MO treatments using examples such as BF3, [HF2]–, XeF2 and SF6. Chapter 5 is a stand-alone chapter dealing with the structures and energetics of solids. Although most students will have a grounding in close-packing of spheres, Chapter 5 assumes little knowledge and starts by covering ccp, hcp, simple cubic and bcc packing, interstitial sites and coordination numbers. From there we look at the structures of metals, and how packing of spheres can be applied to systems such as H2 where the molecules are freely rotating. The bonding in metals is discussed in terms of simple band theory and the discussion leads to differences between metals, semiconductors and insulators. The chapter then moves to a discussion of lattice energies – electrostatic model and Born-Haber cycles – and examples of the applications of lattice energies are discussed in detail. Chapters 6-8 could be used to provide material for one block of lectures, or for two or three shorter modules: the general theme of these chapters is “chemistry in aqueous and non-aqueous media, and redox chemistry”. Chapter 6 covers aqueous solution chemistry of acids, bases and ions from a physical inorganic standpoint. A brief review of pH calculations is given as part of the introduction to acids and bases. While Inorganic Chemistry generally makes use of the assumption that in dilute solutions, concentration ≈ activity, Section 6.3 introduces more rigorous concepts – activity, standard states of solution species, and the difference between molarity and molality. The remainder of Chapter 6 looks at ions in solution, amphoteric behaviour, solubility of salts, sparingly soluble salts, common-ion effect, and concludes by introducing the formation of complexes and stability constants. The theme of Chapter 7 is redox chemistry; the chapter begins with a short review of oxidation states (practice in using them is given in the end of chapter problems). The thermodynamics of redox reactions is treated rigorously, beginning with halfcells and galvanic cells and the Nernst equation. The effects of cell conditions on E values is illustrated with a range of examples. Potential diagrams and Frost-Ebsworth diagrams (the latter being a new feature in the 2nd edition of the book) are introduced, and their uses are illustrated. The chapter also looks at the connections between values of Eo and various thermodynamic quantities. Finally, the use of

7 redox reactions to extract metals from their ores is described and Ellingham diagrams are exemplified. The coverage of non-aqueous solvents in Chapter 8 is introduced with a discussion of relative permittivity, solvent-oriented acid-base behaviour, self-ionization, and levelling and differentiating effects. The remainder of the chapter deals with specific non-aqueous solvents and their uses: liquid NH3, liquid HF, H2SO4, HSO3F, BrF3, N2O4 and representative ionic liquids and supercritical fluids. The latter topic is new to the 2nd edition and focuses mainly on supercritical CO2 and H2O and on their laboratory and commercial applications. Chapters 9-18 deal with the descriptive chemistry of hydrogen, the s-block metals and the p-block elements; the final chapter is this group covers organometallic chemistry of the main group elements. Recent advances have been included throughout and material has been thoroughly updated in going from the 1st to 2nd editions of Inorganic Chemistry. Each of Chapters 9-18 is self-contained, and the choice of material for lectures can be tailored to meet the requirements of a particular course. Suggestions are: • A detailed course may be constructed by working through Chapters 9-18 sequentially. • A “Hydrogen and s-Block” course could be built upon Chapters 9, 10, 11 and part of 18; the organometallic chapter contains a general introduction and then is organized by group. • A “p-Block” course could draw on material from Chapters 12-17 and part of Chapter 18. Chapters 19-23 are concerned with d-block metal chemistry. The suggested presentation of this material is on a modular basis: Modules 1 and 2 could clearly be combined, as could Modules 3 and 4. Some lecturers may prefer to incorporate Module 3 with Module 2, and thereby use the descriptive first-row chemistry to exemplify principles. • Module 1: “Principles of coordination chemistry” uses material from Chapter 19 and the first part of Chapter 20. This covers ground state electronic configurations of the d-block metals, an overview of typical properties, coordination numbers, isomerism, crystal field theory (octahedral, tetrahedral, square planar and other fields) and the use of MO theory in octahedral complexes. • Module 2: “Advanced coordination chemistry” drawn from Chapter 20 and covering electronic spectra, magnetism, ligand field stabilization energies and thermodynamic aspects including the Irving-Williams series. • Module 3: Descriptive chemistry of the first row d-block and applications of principles of coordination chemistry, draws on the content of Chapter 21. • Module 4: “The heavier d-block metals” – Chapter 22 deals with the second and third row metals and themes could be built around metal-metal bonding, metal halide clusters, polyoxometallates, trends in oxidation states, high coordination numbers, contrasting behaviour of the first and heavier metals in each triad. • Module 5: “Organometallic chemistry of the d-block” – Chapter 23 begins with an overview of ligand types, and then deals with the 18-electron rule (assuming a knowledge of the MO theory and introduction to π-acceptor ligands covered in Chapter 20 and Module 1). Binary metal carbonyls are discussed (structures, synthesis and physical properties) and the limitations

8 of the 18-electron rule in high nuclearity clusters leads to total electron counts for single and condensed clusters. Organometallic reaction types are then discussed, and this progresses to detailed chemistry of different types of organometallic compounds, categorized by organic ligand. Chapter 24 deals with the f-block metals and is a stand alone chapter; it is assumed that this module would not be covered until after a study of the d-block. The chapter looks at the metals, coordination chemistry and the organometallic chemistry of the lanthanoids, and then moves to the actinoid metals and their coordination and organometallic complexes with an emphasis on thorium, uranium and (to a lesser extent) plutonium. Chapters 25-28 are “Special Topics” and should be suited for final year undergraduate or graduate courses. The topics have been chosen to meet current needs. Chapter 25 – “d-Block metal complexes: reaction mechanisms” Chapter 26 – “Homogeneous and heterogeneous catalysis” including details of selected industrial processes. Chapter 27 – “Some aspects of solid state chemistry” – rather than give detailed theory bordering on physics, the object of this chapter is to illustrate the applications of materials and development of CVD processes. Chapter 28 – “The trace metals of life” covers metal storage and transport, dealing with O2, biological redox processes, and Nature’s Lewis acid, Zn2+. The material in this chapter has been updated to take account of recent results on the studies of, for example, nitrogenase. Accompanying Solutions Manual by Catherine E. Housecroft The 2nd edition of Inorganic Chemistry is accompanied by a new edition of the Solutions Manual written by one of the authors of the main text (see http:// www.pearsoned.co.uk/housecroft for marketing information). The Solutions Manual provides detailed answers to all the end of chapter problems in the main text. The book complements the main text, and is organized by Chapter. It is heavily illustrated, but uses diagrams that can be readily reproduced by students in examinations. • Where problems involve calculations, detailed working is given along with hints on problem solving, and common sources of error. • The answers to problems which ask for predictions of reaction products give full equations and explanations of the types of reactions or hints on how to arrive at sensible products. • Answers to problems that require an essay or discussion are usually formatted as a series of bullet points, thereby providing an essay plan around which a student can build an answer with reference to appropriate (cross referenced) sections of the main text.

Accompanying Website Visit the Website that has been designed to accompany Inorganic Chemistry – it can be accessed through: http://www.pearsoned.co.uk/housecroft

9 The site is divided into sections: (1) “About the Book” gives general marketing information; (2) a section for Students, which is subdivided by chapter and features self-testing multiple choice questions, and 3D-structures that can be opened and rotated in CHIME; (3) a section for Lecturers which includes Powerpoint files of figures and tables from the main text. Other Websites of general use for Lecturers The following Websites are useful sources of general data. For a table of a visual interpretation of the elements: http://www.chemsoc.org/viselements/

For general information and data for the elements http://www.webelements.com

For physical data: http://physics.nist.gov/cuu/Constants http://webbook.nist.gov/chemistry http://www.tulane.edu/~bmitche/book/metals/m_thermo.html

For general teaching material: http://www.umsl.edu/divisions/artscience/chemistry/books/welcome.html

Viewing atomic orbitals in 3D: http://www.shef.ac.uk/chemistry/orbitron

For NMR, MS and IR data of organic compounds: http://www.aist.go.JP/RIODB/SDBS/menu-e.html

For photographs of and data on minerals: http://mineral.galleries.com/default.htm Historical papers in chemistry: http://webserver.lemoyne.edu/faculty/giunta/papers.html