CHEM 495 TRANSITION METAL CHEMISTRY Credits 3.00 Fall 07
Lon J. Wilson |
Andrew R. Barron
|
Butcher Hall Rm. 353 |
Butcher Hall
Rm. 410
|
Ext. 3268 |
Ext. 5610
|
Office Hours: By appointment |
Office Hours:
By appointment
|
Text book. "Advanced Inorganic Chemistry" (6th edition) By Cotton, Wilkinson, Murillo, Bochmann,published by Wiley Interscience
The first part of Chemistry 495 is a survey course dealing with important topics in transition metal coordination chemistry. It will cover the general topics outlined below. There will be one closed-book examination during the week of October 6. There will not be a comprehensive final examination at the end of the semester. Two or three homework assignments will be assigned and answer keys distributed. Homework will not be graded, but homework-like problems will appear on the examination.
General
Topics
Transition Metal Coordination Compounds
Bioinorganic Chemistry (Introductory Topic)
Syntheses
Nomenclature, Structures and Geometries
Molecular and Point Group Symmetries
Bonding: Crystal Field Theory
Ligand Field Theory
Reactions and Mechanisms
Magnetism
Electronic Spectroscopy (d Æ d)
Transition Metal Chemistry
2.2.2. Dissociation constants and cone angle values for phosphine complexes of nickel
3.1. Carbonyls
3.2. Dinitrogen
3.3. Phosphines
4. Consequences of p-Acidity
4.1. General effects on complex
4.2. Structural effects on the ligand
4.3. Spectroscopic effects on the ligand
4.4. Trans-influence
4.5. Trans-effect
5. The only 6 Reactions Generally Required for Transition Metal Chemistry Mechanisms
5.1. Ligand Association
5.2. Ligand Dissociation
5.3. Migratory Insertion
5.4. Migratory Elimination/b-hydride elimination
5.5. Oxidative Addition
5.5.1. Requirements for oxidative addition
5.5.2. Mechanism of oxidative addition
5.5.2.1. Concerted Addition, e.g., H2
5.5.2.2. Ionic addition, e.g., HCl and HBr (polar solvents)
5.5.2.3. SN-2 type addition, e.g., RCl
5.5.2.4. Radical addition, e.g., RBr and RI
5.6. Reductive elimination
6. Why homogeneous?
6.1. Selectivity
6.2. Activity
6.3. Ease of modification
6.4. Ease of study
7. Why Transition Metals?
7.1. Bonding ability
7.2. Catholic choice of ligands
7.3. Ligand effects
7.4. Variability of oxidation state
7.5. Variability of coordination number
8. Requirements for Catalysis
8.1. High lability of ligands
8.2. Ability to change coordination number
8.3. Ability to change oxidation state
9. Homogeneous Catalyst Systems in Operation
9.1. Isomerization
9.2. Hydrogenation
9.3. Carbonylation
9.4. Hydroformylation
9.5. Oligomerization
9.6. Polymerization
9.7. Oxidation
9.7.2. Heterolytic - metal catalyzed (ligand activation)
9.8. Metathesis
HANDOUTS
2000,
Practice Test
2000,
Test 2001,
Test 1
2001,
Test 1 Answers
2001,
Test 2 (answers to follow)