Chemistry 416 Syllabus Fall 2011

[section in Miessler&Tarr]
I. Introduction: Why transition metal chemistry? [Chapter 1]
II. Brief Review [Chapter 2]
electronic configurations, valence electrons, orbitals, oxidation states
trends in: electronegativity, radii, ionization energies, redox reactions
III. Fundamentals of metal complexes: metals and ligands [Chapters 6,9]
A. Metal ions as Lewis acids the importance of the empty metal s orbital
Review: Acidity, hydrolysis of cations, Lewis acids and bases
B. Octahedral complexes, isomerism [9-1,2,3; 9-4-4]
C. Types of ligands anything with a valence pair of electrons can serve as a ligand
1. hard and soft acids and bases [6.3]
2. organometallic ligands just a little (covered in Chem 417) [13.1-13.4]
IV. Bonding in transition metal complexes [Chapter 10]
A. Crystal field theory for octahedral complexes
1. spectrochemical series
2. high spin vs. low-spin
3. ligand field stabilization energies (LFSE)
B. Molecular orbital picture of metal complexes
Brief review of bonding and Molecular Orbital theory [Chapter 5]
C. -bonding in metal complexes [10-3-4, 10-4-2,3]
1. weak -donor ligands
2. -acceptor ligands [13-4-1,2]
V. Non-octahedral coordination geometries [Chapter 9]
A. The Jahn-Teller effect [10-5]
B. Non-octahedral coordination geometries: the18 e rule [13-3]
VI. Descriptive chemistry of the d block
A. Redox Potentials
B. High oxidation states and strong -donor ligands
C. Intermediate oxidation states for 3d elements
D. Biological transition metal chemistry [Chem 419] [Chapter 16*]
E. 4d and 5d elements: large ligand field splittings and the 18-e rule
F. Organometallic compounds [Chem 417] [Chapters 13,14*]
G. Metal-metal bonding [15-3]
*will do only a little of these chapters
VII. Bonding in more detail
A. Molecular shape and symmetry [Chapter 4]
1. Symmetry analysis; introductory group theory
2. Applications of symmetry analysis
3. Symmetries of orbitals
B. Ligand field theory and electronic spectroscopy [Chapter 11]
1. Electronic structure of free atoms and ions: the importance of electron-electron repulsion
2. Splitting of free-ion terms.
Weak-field Strong field correlation diagrams
Tanabe-Sugano diagrams
3. Electronic spectra
d-d transitions
charge transfer transitions
4. Luminescence
VII. Reactions of Transition Metal Complexes [Chapter 12]
A. Ligand substitution [12-2 12-7]
1. Square planar complexes
2. Octahedral complexes
B. Redox reactions [12-8]
1. Inner-sphere vs. outer-sphere reactions
2. Marcus theory of electron transfer (if theres time and interest)
C. Photochemistry
Chemistry 416, Fall 2011 -- Logistics

Class meets: MWF 11:30 - 12:20 in Bagley 260

Recommended Text: Inorganic Chemistry, 3rd Ed., Gary L. Miessler and Donald A. Tarr
Web Site: https://catalyst.uw.edu/workspace/chemfa11/24304/
or you can get there via the UW Chem site, http://depts.washington.edu/chem/courses
Discussion Board: https://catalyst.uw.edu/gopost/board/jmmayer/23662/
Reserve Books:
Shriver and Atkins Inorganic Chemistry, 4th Ed., Peter Adkins et al.
Ligand Substitution Processes Cooper H. Langford and Harry B. Gray; 541.39 L263L
Advanced Inorganic Chemistry F. A. Cotton and G. Wilkinson, 5th ed. QD151.2. C68
Chemistry of the Elements N.N. Greenwood and A. Earnshaw QD466.G74 1984
Ligand Field Theory and its Applications B.N. Figgis, M.A. Hitchman; QD475.F54 2000
Chemical Applications of Group Theory F. Albert Cotton; QD461.C65 1990
Inorganic and Organometallic Reaction Mechanisms Jim D. Atwood; QD501.A89

Office hours:
Jim Mayer, New Chemistry Building 304D;
543-2083; mailbox # 38; mayer@chem.washington.edu
office hours: Monday 2:00-3:00; Wednesday 10:00-11:00, and by appointment.
TA: Amanda Weaver, New Chemistry Building 211;
616-2974; mailbox #282; alw285@uw.edu
office hours: Tues & Thurs 12:30 - 1:30 pm in Bagley 330 (Chem. Study Center) or by appt.
Grading and Exams:
Grades will be determined on the basis of scores for two midterm exams, the final exam, and
about nine graded problem sets. There will be no makeup exams; if you will miss an exam,
please see Professor Mayer as soon as possible.
Problem sets 6%
Midterm I 23% Monday, October 24
Midterm II 23% Friday, November 18
Final Exam 48% 2:30-4:20 p.m. Wednesday, December 14
Anyone who gets 85% or more of the points available for the class will get a 4.0 grade.
The mean and median grades for this class have historically been about 3.1-3.2. This years
grades will likely be in this range as well, unless this class is unusually strong (or poor).
You are strongly encouraged to work together on the problem sets, although each student is
required to turn in answers in his/her own words. No credit to either paper will be given for
duplicate answers. Copying of answers from other students or any other sources will be
considered plagiarism and reported to the UW committee on academic misconduct.
Disabled Students: If you would like to request academic accommodations due to a disability, please
contact Disabled Student Services, 448 Schmitz, 543-8924 (V/TDD). If you have a letter from
Disabled Student Services indicating you have a disability that requires academic accommodations,
please meet with Professor Mayer as soon as possible to discuss the accommodations you need.
Questions, complaints, comments, suggestions, etc.: Please raise any issues that come up -- the
more communication the better -- with the Professor or the TA, in person (at office hours, in,
before, or after class) or via a note in his/her mailbox. Notes can be signed or anonymous.