Inorganic Chemistry 3 2013_2014

COURSE OUTLINE – Inorganic Chemistry 3 Instructors: M. Casarin ([email protected]) & S. Gross ([email protected]) Examination Board: Maurizio Casarin, Silvia Gross, Luciano Pandolfo & Mauro Sambi Overview: Systematic presentation of the applications of group theory to the inorganic chemistry. Emphasis on the formal development of the subject and its applications to the physical methods of inorganic chemical compounds. Against the backdrop of electronic structure, the electronic, vibrational, and magnetic properties of transition metal complexes are presented and their investigation by the appropriate spectroscopy described. The laboratory session will be devoted to improve the students practical skills in the synthesis of different molecular and bulk inorganic compounds, as well as in their spectroscopic characterization. The following topics will be considered: 1. Symmetry elements and operations 2. Operator properties and mathematical groups 3. Irreducible representations and character tables 4. Molecular point groups 5. LCAO and Hückel theory 6. General electronic considerations of metal-ligand complexes 7. Frontier molecular orbitals of σ-donor, π-donor and π-acceptor ligands 8. Octahedral ML6 σ complexes 9. Octahedral ML6 π complexes 10. Selection rules for electronic spectroscopy 11. Molecular Vibration 12. The weak field 13. The strong field 14. Tanabe-Sugano diagrams 15. Descent in symmetry 16. Spin orbit coupling, double groups, and ligand fields 17. Magnetic susceptibility and the Van Vleck equation 18. Transition metal magnetism Textbooks: G. L. Miessler and D. A. Tarr, Inorganic Chemistry, 4th ed. (Upper Saddle River, NJ: Pearson Prentice Hall, 2011) R. L. Carter, Molecular Symmetry and Group Theory (New York: John Wiley & Sons, 1998) U. Schubert, N. Hüsing, Synthesis of inorganic materials, 2nd ed., (Weinheim Wiley VCH, 2004) References: • J. Barrett, Atomic Structure and Periodicity (The Royal Society of Chemistry, 2002) • I. B. Bersuker, Electronic Structure and Properties of Transition Metal Compounds (New York: John Wiley & Sons, 2010) • D. M. Bishop, Group Theory and Chemistry (Oxford: Clarendon press, 1973) • J. K. Burdett, Molecular Shapes, Theoretical Models of Inorganic Chemistry, New York: John Wiley & Sons, 1980) • R. L. Carter, Molecular Symmetry and Group Theory (New York: John Wiley & Sons, 1998) • F. A. Cotton, Chemical Applications of Group Theory, 3rd ed. (New York: Wiley, 1990) • B. N. Figgis, Introduction to Ligand Fields (New York: Interscience Publishers,1967) • N. N. Greenwood and A. Earnshaw, Chemistry of the Elements (Oxford, Butterworth and Heinemann, 1998) • J. S. Griffith, The Theory of Transition Metal Ions (Cambridge, University Press, London, 1961) • C. E. Housecroft and A. G. Sharpe, Inorganic Chemistry, 2nd ed. (Edinburgh Gate, Pearson Education Limited, 2005) • J. E. Huheey, E. A. Keiter, and R. L. Keiter, Inorganic Chemistry, 4th ed. (New York: Harper Collins, 1993) • M. Lesk, Introduction to Symmetry and Group Theory for Chemists, (New York: Kluwer Academic Publishers, 2004) • G. L. Miessler and D. A. Tarr, Inorganic Chemistry, 4th ed. (Upper Saddle River, Pearson Prentice Hall, 2011) • K. F. Purcell and J. C. Kotz, Inorganic Chemistry (Saunders, 1977) • K. F. Riley, M. P. Hobson and S. J. Bence, Mathematical Methods for Physics and Engineering (Cambridge, University Press, London, 2006) • J. H. van Vleck, The Theory of Electric and Magnetic Susceptibilities (Oxford, Clarendon Press, 1932)

Website:

A website will be maintained through the “Dipartimento di Scienze Chimiche” website (http://www.chimica.unipd.it/maurizio.casarin/pubblica/casarin.htm). Handouts, laboratories, and other information will be posted on the website as .pdf files. The course website also contains links to the electronic reserves, the ChemDraw download, and other relevant websites.

Discussion:

Discussion sessions are an integral component of the course. The discussion sessions will focus on advanced problems and the chemical literature, but there will also be the opportunity for student questions pertaining to practice problems or any aspect of the course. Most weeks there will be specific work to be prepared for the discussion session, which will be noted on the weekly handout and posted on the course website; discussion preparation and discussion session work is in lieu of graded homework assignments, so this work should be taken as seriously as one would consider graded assignments. Solutions to discussion questions will be posted on the course website.

Exams:

There will be six two-hour written exams (two at the end of the first semester, two at the end of the second semester, two before the new academic year starting).

Laboratory:

Attendance at all laboratory sessions is required, and on-time arrival is essential. Experiments and theoretical background for the laboratory sessions will be introduced in dedicated lectures. Laboratory lecture notes (dispense) will be provided by the laboratory instructors. Laboratory safety is of utmost importance. Laboratory safety issues will be reviewed during the first laboratory sessions. Each student is required to provide her/his own laboratory notebook, which should contain bound, sequentially numbered pages (loose-leaf binders and spiral-bound notebooks are not acceptable); a standard composition book is sufficient, since duplicate pages are not required. It is acceptable to continue to use a laboratory notebook from a previous chemistry course if sufficient space is available. Notebooks will be collected twice for evaluation. Written reports (a template will be provided) are required for all experiments and should be submitted electronically after the class or laboratory period on the days indicated; there will be a penalty for late submission without prior approval.

Final Grade:

Exams count as 75% of the final grade, and discussion and laboratory work constitute the remaining 25% of the final grade.

Intellectual Responsibility: Students enrolled in Inorganic Chemistry 3 are expected to abide by the “Regolamento delle carriere degli studenti” of the University of Padova. Particular attention should be paid to the items 23 (Deontologia Studentesca) and 24 (Provvedimenti Disciplinari). The specific implications of the statement for Inorganic Chemistry 3 are: 1. Students are encouraged to study together and to discuss the course material and laboratory experiments, but all work submitted for evaluation must represent the student’s own work and reflect her/his understanding of the material. 2. In-class exams must be worked individually during the allotted time, with no resources other than those provided with the exam. No discussion or other communication with other students will be permitted during exams. The exams will state clearly which reference materials, if any, may be used during the exams. 3. Students are strongly invited to produce original written reports, using high level references (scientific journals or textbooks) and disregarding unreliable sources as Wikipedia. Copying and plagiarism (copying somebody’s words, written texts, ideas, figures without quoting the sources) are, according to international legislation, a crime and are punished by the Italian law (Legge 22 aprile 1941 n. 633).