CHEM495

CHEM 495 TRANSITION METAL CHEMISTRY

CHEM 495 TRANSITION METAL CHEMISTRY Credits 3.00 Fall 00

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

Prereq- CHEM 360

001 DH1042 - MWF 10:00AM - 10:50AM

Andrew R. Barron and Lon J. Wilson

Course Outline
Handouts
Exams and Assignments

Course Outline

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

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 &endash; 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.

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Handouts

Cone Angle

Dissociation Constants

Exams and Assignments

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