LECTURER(S) / Afif M. Seyam / Email:
CREDITS / 3 / PRE-REQUISITE(S)
DURATION OF COURSE / 16 weeks
OBJECTIVES:
The main objectives of the course are:
1. Understand the present knowledge about the chemistry of organo-f-element compounds, synthetic methods, structural investigations, and chemical reactivity.
2. Understand the general chemical and physicochemical characteristic of the f-metal ions.
3. Understand the kinetics and mechanisms of reactions.
4. Understand the predictive power of metal-ligand bond desruption enthalpies.
5. Applications in organic synthesis and homogeneous catalysis.
INTENDED LEARNING OUTCOMES:
Subject specific skills:
1. Know how to synthesize and characterize f- element compounds.2. Write a mechanism for a stoichiometric and catalytic reactions.
3. Predict the feasibility of a chemical reaction.
4. Draw the structure of organo-f- element compounds and understand bonding.
5. Discuss the chemistry of organo-f- element compounds.
Core Academic skills: At the end of the course, students are expected to gain knowledge and skills about the synthetic methods, structure and reactivity, and manipulation of air- and moisure- sensitive compounds using Schlenk and glovebox techniques.
Personal and Key skills: At the end of the course, students are expected to know:
1. How to prepare organometallics.
2. The different techniques used in characterization.
3. How to use thermochemical data in predicting unknown reactions.
4. How to study fluxional behavior.
LEARNING/TEACHING METHODS: lectures, group discussions, seminars by indivisual students to encourage developing skills of self expression.
Teaching tools include transperancies, slides, handouts, and case study critical review.
ASSIGNMENTS: Each student will choose a topic on which he explores literature and the internet and then write a critically reviewed report and give a seminar.
ASSESSMENT: Mid Term Exam: 30%, Assignments & Problem Solving: 30%, Final Exam: 40% = 100%.
Course Description Template For Graduate Studies
Faculty: Faculty of Graduate Studies Lecture Room: C 107
Department: Department of Chemistry First Semester 2008/2009
Syllabus
Week / Topic / Hrs / Comments1 / GENERAL PROPERTIES OF f-ELEMENTS / 2
SCANDIUM, YTTRIUM, AND THE LANTHANIDES
2 / Carbonyls and Cyclopentadienyl Compounds / 4
3
4 / Modified Cyclopentadienyl Compounds and Cyclopentadienyl - like Compounds / 4
1
5 / Cyclooctatetraenyl Compounds / 2
5 / Allyls, and Hydrocarbyl Compounds / 2
6 / Hydrides, Arenes, and Fullerene Compounds / 1
6 / Heterobimetallic Compounds / 1
7 / Organic Synthesis and Catalysis / 2
7 / Zero Oxidation State Complexes / 1
ACTINIDES
8 / Carbonyls and Cyclopentadienyl Compounds / 39 / Modified Cyclopentadienyl Compounds and Cyclopentadienyl - like Compounds / 2
9 / Cyclooctatetraenyl Compounds / 2
10 / Allyls, and Hydrocarbyl Compounds / 1
10 / Hydrides, Arenes, and Heterobimetallic Compounds / 1
Mid Term Exam
/ 111 /
Tris (h5-cyclopentadienyl)uranium(IV) Hydrocarbyls
/ !11 / Bis (h5-pentamethylcyclopentadienyl) Actinide Hydrocarbyl and Hydride Compounds
/ 2
12 / Thermochemical Aspects of Metal-Legands Bond Desruption Enthalpies and Stoichiometric and Catalytic Organometallic Chemistry
/ 3
13 /
Photoelectron Spectroscopy of Organo-f-Elements
/ 113 /
Ring-Opening Ziegler Polymerization of Methylenecycloalkanes
/ 114 /
Organolanthanide-Catalyzed Hydroamination/Cyclization. Synthesis of Naturally Occurring Alkalloids
/ 315 /
Life Beyond Metallocenes
/ 216 /
Olefin Polymerization Catalysis
/ 316 /
Seminars
/ 2INDICATIVE BASIC READING LIST / RELATED WEBSITES
1. Marks,T. J.; Ernst, R. D. “Scandium, Yttrium and the Lanthanides and Actinides”, in, “Comprehensive Organometallic Chemistry”, Abel,E. W.; Stone, F. G. A.; Wilkinson, G. ed., Pergamon, 3, 1982, 174-270.2. Edelman, F. T. “Scandium, Yttrium and the Lanthanides and Actinides”,
in, “Comprehensive Organometallic Chemistry II”, Abel, E. W.; Stone,
F. G. A.; Wilkinson, G. ed., Pergamon, 4, 1996, 12-212.
3. Fagan, P. J.; Manriquez, J. M.; Maatta, E. A.; Seyam, A. M.; Marks, T. J., "Synthesis and Properties of Bis (h5-pentamethylcyclopentadienyl) Actinide Hydrocarbyls and Hydrides. A New Class of Highly Reactive f-Element Organometallic Compounds", J. Am. Chem. Soc., 1981, 103, 6650-6667.
4. Marks, T. J. Seyam, A. Kolb, J. R., "Synthesis, Chemistry, and Spectroscopy of Some, Tris (h5-pentahaptocyclopentadienyl) Uranium (IV) Alkyl and Aryl Compounds", J. Am. Chem. Soc., 1973, 95, 5529-5539.
5. Schock, L. E.; Seyam, A. M.; Sabat, M.; Marks, T. J., " A new Approach to Measuring Absolute Metal-Ligand Bond Disruption Enthalpies in Organometallic Compounds. The [CH3)3SiC5H4]3U- System ", Polyhedron, 1988, 7, 1517-1529.
6. Marks, T. J.; Gagne, M. R.; Nolan, S. P.; Schock, L. E. ;Seyam, A. M. ; Stern, D. , "What Can Metal-Ligand Bonding Energetics Teach us About Stoichiometric and Catalytic Organometallic Chemistry", Pure and Appl. Chem. , 1989, 61, 1665-1672.
7. Gagne, M. R.; Nolan, S. P.; Seyam, A. M.; Stern, D.; Marks, T. J., "Thermochemical Aspects of Organotransition Metal Chemistry. Insights Provided by Metal-Ligand Bond Enthalpies", for "Metal-Metal Bonds and Clusters in Chemistry and Catalysis", Fackler, J. P., ed., Plenium Pubs, New York, 1990.
8. Marks, T. J.; Seyam, A. M.; Wachter, W. A., "Chlorotris- (h5-Cyclopentadienyl) Complexes of Uranium (IV) and Thorium (IV)," in "Reagents for Transition Metal Complex and Organometallic Synthesis", Angelici, R. J.; Editor-in-Chief, Inorg. Syn., 1990, 28, 300-304.
9. Gulino, A.; Cilibello, E.; Di Bella, S.; Fragala, I.; Seyam, A. M.; Marks, T. J., "Photoelectron Spectroscopy of f-Element Organometallic Complexes. 8. DV-Xa and Gas-Phase UV Photoelectron Spectroscopic Investigation of the Electronic structure of Tris (h5- Cyclopentadienyl) Uranium (IV) Complexes ", Organometallics, 1992,11, 3248-3257.
10. Gulino, A.; Di Bella, S.; Fragala, I.; Casarin, M.; Seyam, A. M.; Marks, T. J., " A Comparative Fully Relativistic/ Nonrelativistic First-Principles Xa-DVM and Photoelectron Spectroscopic Investigation of Electronic Structure in Homologous 4f and 5f Tris (h5-Cyclopentadienyl) Metal (IV) Alkoxide Complexes ", lnorg. Chem., 1993, 32, 3873-3879.
11. Jia, L.; Yang, X.; Seyam, A. M.; Albert, I. D. L.; Fu, P. – F.; Yang, S.; Marks, T. J., “ Ring-Opening Ziegler Polymerization of Methylenecycloalkanes Catalyzed by Highly Electrophilic d0/fn Metallocenes. Reactivity, Scope, Reaction Mechanism, and Routes to Functionalized Polyolefins ”, J. Am. Chem. Soc., 1996, 118, 7900-7913.
12. Seyam, A. M.; Stubbert, B. D.; Jensen, T. R.; O’Donnell, J. J., III; Stern, C. L.; Marks, T. J., “Organolanthanide Constrained Geometry Complexes Modified for Catalysis. Synthesis, Structure, and Aminoalkene Hydroamination Properties of a Pyrrolidine-Substituted Constrained Geometry Organolutetium Complex”, Inorg. Chim. Acta, 2004, 357, 4029-4035.
13. Science Finder
14. Roberts, John A. S.; Chen, Ming-Chou; Seyam, Afif M.; Li, Liting; Zuccaccia, Cristiano; Stahl, Nicholas G.; Marks, Tobin J., “ Diverse Stereocontrol Effects Induced by Weakly Coordinating Anions. Stereospecific Olefin Polymerization Pathways at Archetypal Cs- and C1-Symmetric Metallocenium Catalysts Using Mono- and Polynuclear Halo-perfluoroarylmetalates as Cocatalysts”, J. Am. Chem. Soc., 2007, 129(42), 12713-12733.
Office Hours: 11:30-12:30 M&W; 10:00-11:00 Su, Tu.