Download Chemistry 459 ORGANOMETALLIC CHEMISTRY Fall, 2010 J. R.

Chemistry 459
ORGANOMETALLIC CHEMISTRY
Fall, 2010 J. R. Bleeke
Class will meet from 8:37 till 10:00 am in Lab Sciences, Room 301.
BASIC PRINCIPLES
Class 1 Tu
Class 2 Th
Aug. 31
Sept. 2
Oxidation state, d-electron counting, brief survey of ligands
18 e– rule, molecular orbital description of Cr(CO)6
Class 3 Tu
Sept. 7
Class 4 Th
Sept. 9
Pi-backbonding, d-orbital splitting patterns for various
coordination geometries
Cluster electron counting, M-M bonding
SYNTHESIS, STRUCTURE, AND SPECTROSCOPY OF ORGANOTRANSITION METAL COMPLEXES
(A SURVEY OF THE LIGANDS)
Class 5 Tu
Class 6 Th
Sept. 14
Sept. 16
Metal-carbonyl and metal-thiocarbonyl complexes
Phosphine and other phosphorus-containing complexes
Class 7 Tu
Sept. 21
Class 8 Th
Sept. 23
Metal-hydride and metal-dihydrogen complexes, agostic
interactions
Metal-alkyl, metal-acyl, metal-formyl complexes
Class 9 Tu
Class 10 Th
Sept. 28
Sept. 30
Metal-olefin and metal-acetylene complexes
Metal-allyl and metal-cyclopentadienyl complexes, ligands
resembling cyclopentadienyl
Class 11 Tu
Class 12 Th
Oct. 5
Oct. 7
Exam 1
Metal-arene complexes, other cyclic B-hydrocarbon ligands
Class 13 Tu
Class 14 Th
Oct. 12
Oct. 14
Metal-carbenes and metal-carbynes
Metallacycles
Class 15 Tu
Class 16 Th
Oct. 19
Oct. 21
Miscellaneous ligands (N2, NO, O2, CO2)
M-M multiply-bonded species
FUNDAMENTAL REACTION STEPS
Class 17 Tu
Class 18 Th
Oct. 26
Oct. 28
H-H and C-H oxidative addition, reductive elimination
R-X oxidative addition
Class 19 Tu
Class 20 Th
Nov. 2
Nov. 4
Migratory insertion
Nucleophilic addition to CO and olefin ligands
Class 21 Tu
Class 22 Th
Nov. 9
Nov. 11
Exam 2
Nucleophilic addition to allyl and arene ligands
CATALYSIS
Class 23 Tu
Nov. 16
Class 24 Th
Nov. 18
Class 25 Tu
Nov. 23
Hydrogenation of unsaturated substrates, including asymmetric
hydrogenation
Catalytic reactions involving CO (hydroformylation, Reppe rxs.,
Monsanto acetic acid)
Olefin metathesis
No class on Thursday, Nov. 25, Thanksgiving Day
Class 26 Tu
Class 27 Th
Nov. 30
Dec. 2
Epoxidation, including asymmetric epoxidation
Dihydroxylation and aminohydroxylation
Class 28 Tu
Class 29 Th
Dec. 7
Dec. 9
Oligomerization of olefins and dienes
Olefin Polymerization
FINAL EXAM –Friday, December 17, 1:00-3:00 pm
Homework problems will be regularly assigned (see attached sheet) but not collected.
Review sessions will be held before each exam. Each in-class exam is worth 150 points; the
final exam is worth 200 points.
Various supplementary texts are on reserve in the Chemistry Department Library (list
attached). These books may be used in the library during the day or checked out overnight.
For appointments, please see me after class or send e-mail to [email protected]. We will
find a mutually agreeable time to meet.
Chemistry 459
HOMEWORK PROBLEMS
Assignment
Topic
To Be Completed By
___#__________________________________________________
1
Electron counting
Sept. 10
2
M-M bonding
Sept. 17
3
Carbonyls and phosphines
Sept. 24
4
Hydrides
Oct. 1
5
Olefins and acetylenes
Oct. 8
6
Arenes and cyclopentadienyls
Oct. 15
7
Carbenes and metallacycles
Oct. 22
8
M-M multiple bonds
Oct. 29
9
Ligand substitution, oxidative
addition
Nov. 5
10
Migratory insertion
Nov. 12
11
Nucleophilic addition
Nov. 19
12
Catalysis
Dec. 3
13
Olefin Polymerization
Dec. 10
Reserve Books for Organometallic Chemistry
(Chem 459)
1.
Atwood, J.D. Inorganic and Organometallic Reaction Mechanisms
2.
Collman, J.P.; Hegedus, L.S.; Norton, J.R.; Finke, R.G. Principles and Applications of
Organotransition Metal Chemistry
3.
Cotton, F.A. Chemical Applications of Group Theory
4.
Cotton, F.A.; Wilkinson, G. Advanced Inorganic Chemistry
5.
Davies, S.G. Organotransition Metal Chemistry: Applications to Organic Synthesis
6.
Elschenbroich, C.; Salzer, A. Organometallics, A Concise Introduction, 2nd ed.
7.
Haiduc, I.; Zuckerman, J.J. Basic Organometallic Chemistry
8.
Masters, C. Homogeneous Transition-Metal Catalysis - A Gentle Art
9.
Mehrotra, R.C.; Singh, A. Organometallic Chemistry (A Unified Approach)
10.
Parkins, A.W.; Poller, R.C. An Introduction to Organometallic Chemistry
11.
Parshall, G.W.; Ittel, S.D. Homogeneous Catalysis: The Applications and Chemistry of
Catalysis by Soluble Transition Metal Complexes
12.
Pearson, A.J. Metallo-organic Chemistry
13.
Pignolet, L.H. Homogeneous Catalysis with Metal Phosphine Complexes
14.
Yamamoto, A. Organotransition Metal Chemistry: Fundamental Concepts and Applications