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Chemistry 4471: Transition Metals in Catalysis Instructor: Dr. R. J. Puddephatt Office: Room 100, Chemistry Building A. Course Outline 1. Historical introduction to organotransition metal chemistry and catalysis. Qualitative MO theory for complexes. Electron counting rules. 2. Metal carbonyls: Structure and bonding, preparations, reactions. Related B-acceptor ligands. 3. Alkene and alkyne complexes. Structure, bonding, reactivity, role in catalysis. 4. Carbene, vinylidene and carbyne complexes; applications in synthesis. 5. More complex unsaturated organic ligands: 0-allyl, 0-cyclopentadienyl, 0-arene etc. 6. Alkyl and hydride complexes. 7. Migratory insertion, $-elimination and related reactions; role in catalysis. 8. Oxidative addition, reductive elimination, bond activation; role in catalysis. 9. Selected applications in organic synthesis 10. Industrial homogeneous catalysis: hydrogenation, hydroformylation, hydrosilation, oxidation, polymerization of alkenes. Acetic acid synthesis and related catalysis. Asymmetric catalysis. Current challenges. 11. Heterogeneous and hybrid homogeneous/heterogeneous catalysts. B. What is expected of the registrant You are expected to know the concepts and theories used to understand structure, bonding, mechanism, reactivity and catalysis in organotransition metal chemistry. You are also expected to know some descriptive chemistry, especially including applications of organotransition metal complexes in catalysis. C. Textbooks There is no prescribed text for the course. Most textbooks of inorganic chemistry contain useful sections on organometallic chemistry and catalysis. For example: Inorganic Chemistry, by Shriver, Atkins et al., (Freeman) Advanced Inorganic Chemistry, by Cotton and Wilkinson et al., Wiley. There are also several excellent texts on organometallic chemistry and catalysis which are recommended, including: Organometallics, by C. Elschenbroich and A. Salzer, VCH. The Organometallic Chemistry of the Transition Metals, by R.H. Crabtree, Wiley. Fundamental Transition Metal Organometallic Chemistry, by Lukehart, Brooks-Cole. Principles and Applications of Organotransition Metal Chemistry, by Collman, Hegedus, Norton and Finke, University Science Books. Homogeneous Catalysis, by G.W. Parshall, Wiley, NY. D. Evaluation Three in-class tests (15%, 15% and 20%); one final examination (50%). Term tests will be held during the regular lecture period on January 27, February 15 and March 17. If you miss a term test through illness, the weighting of marks will be revised appropriately. There is a three-hour final in the Final Examination period (cumulative, but weighted in favour of the later part of the course which has not been tested previously). Course prerequisite: Chemistry 3371f. Important Announcements: Scholastic offences are taken seriously and students are directed to read the appropriate policy, specifically, the definition of what constitutes a Scholastic Offence, at the following Web site: http://www.uwo.ca/univsec/handbook/appeals/scholastic_discipline_undergrad.pdf Illness or other serious circumstances If you are unable to meet a course requirement due to illness or other serious circumstances, you must provide valid supporting documentation to your instructor (missed assignment deadlines) or the Academic Counselors in the Dean's office (for a missed midterm/exam) as soon as possible and contact your instructor immediately. It is the student's responsibility to make alternative arrangements with their instructor once the accommodation has been approved and the instructor has been informed. In the event of a missed final exam, a "Recommendation of Special Examination" form must be obtained from the Dean's Office immediately. For further information please see: http://www.uwo.ca/univsec/handbook/appeals/medical.pdf A student requiring academic accommodation due to illness, should use the Student Medical Certificate when visiting an off-campus medical facility or request a Records Release Form (located in the Dean's Office) for visits to Student Health Services. The Student Medical Certificate form can be found here: http://www.uwo.ca/univsec/handbook/appeals/medicalform.pdf Students who are in emotional/mental distress should refer to Mental Health@Western http://www.uwo.ca/uwocom/mentalhealth/ for a complete list of options about how to obtain help. For Student Services see: https://studentservices.uwo.ca/secure/index.cfm Since the policy on medical illness explicitly states that documentation should go to the academic counselling office and forbids instructors from collecting medical documentation, we are not able to deal with appeals made on medical grounds at the departmental level. Please follow the Policy on Accommodation for Illness, and contact the Academic Counselling Office of your home Faculty: http://www.uwo.ca/univsec/pdf/academic_policies/appeals/accommodation_illness.pdf Accessibility Please contact the course instructor if you require material in an alternate format or if any other arrangements can make this course more accessible to you. You may also wish to contact Services for Students with Disabilities (SSD) at 661-2111 ext. 82147 if you have questions regarding accommodation. Link to the website for Registrarial Services: http://www.registrar.uwo.ca Learning Outcomes • Identify and explain different bonding types found in organometallic complexes that are relevant to catalysis. • Sketch and label individual reaction steps that comprise well-known catalytic cycles. • Justify observed catalytic performance based on known structure and bonding properties of the catalyst intermediates.