Structure, bonding and reactivity of coordination and organometallic compounds; ligand field theory; electronic spectroscopy; magnetism; reaction mechanisms; catalysis.
Prereq- CHEM 360
GRB 212W - MWF 10:00AM - 10:50AM
Lon J. Wilson and Andrew R. Barron

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


 Course Syllabus

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)


Nomenclature, Structures and Geometries

Molecular and Point Group Symmetries

Bonding: Crystal Field Theory

Ligand Field Theory

Reactions and Mechanisms


Electronic Spectroscopy (d Æ d)

Transition Metal Chemistry

1. Metal Characteristics
1.1. Electronic Effects
1.1.1. Formal oxidation state 1.1.2. Valence shell electron count
1.2. Steric Effects
1.2.1. Coordination number
2. Ligand Characteristics
2.1. Electronic Effects 2.1.1. Purely sigma-donor2.1.2. p-acid ligands
2.2. Steric Effects - Cone angle
2.2.1. Ref. Chem. Rev., 1977, 77, 313 and Inorg. Chem., 1978, 17, 2965

2.2.2. Dissociation constants and cone angle values for phosphine complexes of nickel


3. p-Acid Ligands

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

5.3.1. Ref. Angew. Chem., 1977, 16, 299, J. Chem. Soc., Dalton Trans., 1975, 774

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 Concerted Addition, e.g., H2 Ref. J. Am. Chem. Soc., 1976, 98, 4665 and 6978 Ionic addition, e.g., HCl and HBr (polar solvents) SN-2 type addition, e.g., RCl 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

9.7.1. Homolytic

9.7.2. Heterolytic - metal catalyzed (ligand activation)

9.8. Metathesis





Exams and Assignments


Previous Years Exams with Answers:

2000, Practice Test
2000, Test 2001, Test 1
2001, Test 1 Answers
2001, Test 2 (answers to follow)

Return to Barron Group Home Page