CHEM 495 TRANSITION METAL CHEMISTRY Credits 3.00 Fall 03

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

Lon J. Wilson and Andrew R. Barron

• Course Syllabus
• Course Outline
• Handouts
• Exams and Assignments 
• Previous Years' Exams with Answers

 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)

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)

Chemistry 495 (Part One) Reading Schedule

Transition Metal Chemistry

 

Week 1- Aug. 25	Bioinorganic Handout
Week 2 - Sept. 1	Chapter 1 CWMB (p. 3-47)
Week 3 - Sept. 8	Chapter 16 (p. 633-691)
Week 4 - Sept. 15	Chapter 17 (p. 692-736)
Week 5 - Sept. 22	Chapter 17 (p. 736-816)
Week 6 - Sept. 29	Chapter 17 (p. 816-876)
Week 7 - Oct. 6	Chapter 19 (p. 1108-1129) and Chapter 20 (p. 1130-1164)
Week 8 - Oct. 13	Schedule for 2nd half of this Course will be posted soon

 

Course Outline October 14 through December 4, 2003 (2nd Half of Semester)

 

 

1. Metal Characteristics

 

1.1. Electronic Effects

1.2. Steric Effects

 

 

2. Ligand Characteristics

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

HANDOUTS

Cone Angle	Dinitrogen
Dissociation Constants	p-back Donation
p-Acids Ligands	H2 Addition
Trans-Influence	Alkene M-H
Trans-Effect	Examples of Chiral Phosphines
Oxidative Addition	Polypropylene
Carbonyls

 

Exams and Assignments

 

2003: Assignment Dec. 1, 2003; due Dec. 15, 2003

 

 

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Previous Years Exams with Answers:

 

2000, Practice Test

2000, Test

2001, Test 1

2001, Test 1 Answers

2001, Test 2 (answers to follow)

est 2

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