CHEM 495 TRANSITION METAL CHEMISTRY Credits 3.00 Fall 01

Structure, bonding and reactivity of coordination and organometallic compounds; ligand field theory; electronic spectroscopy; magnetism; reaction mechanisms; catalysis.

Prereq- CHEM 360

001SS 106 - MWF 10:00AM - 10:50AM

Andrew R. Barron and Lon J. Wilson

• Course Outline
• Handouts
• Exams and Assignments 

Text book. This course has no text book, however, it is recommended that students obtain a copy of any Edition of "Advanced Inorganic Chemistry" By Cotton and Wilkinson, published by Wiley

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-donor

2.1.2. 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

5.5.2.1. Concerted Addition, e.g., H2

5.5.2.1.1. Ref. J. Am. Chem. Soc., 1976, 98, 4665 and 6978

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

9.7.1. Homolytic

9.7.2. Heterolytic - metal catalyzed (ligand activation)

9.8. Metathesis

 

If you have a documented disability that will impact your work in this class, please contact me to discuss your needs. Additionally, you will need to register with the Disability Support Services Office in the Ley Student Center.

 Return to Top of Page

Cone Angle

Dissociation Constants

p-Acids Ligands

Trans-Influence

Trans-Effect

Oxidative Addition 
Carbonyls
Dinitrogen
p-back Donation
H₂ Addition
Alkene M-H

Examples of Chiral Phosphines

Polypropylene

 

Exams and Assignments

TEST #1: CHEM 495 TRANSITION METAL CHEMISTRY – FALL 2001
Due Nov 26th, 2001

ANSWERS TO TEST #1 are here

 

TEST #2: CHEM 495 TRANSITION METAL CHEMISTRY – FALL 2001
Due December 24th, 2001

 

---

Following are assignments or test questions and answers from the Fall, 2000 course. New assignments and tests will be distributed for the Fall, 2001 course.

Assignment 1 (Not for Credit)

Assignment 2

Return to Top of Page

Return to Barron Group Home Page