Southern Connecticut State University Department of Chemistry

Southern Connecticut State University Department of Chemistry Instructor: Dr. M. J. Gerald (Gerry) Lesley Office: Jennings Hall 308 Telephone: (203) 392-6262 or ext: 26262 on campus E-mail: Lesleym1@Southernct.edu Title: CHE 532 - Advanced Inorganic Chemistry I Prerequisite: CHE 435 Lectures: W: TBA (Jennings Hall 306) Office Hours: TBA Course Description: Presentation of the theoretical and descriptive aspects of the chemical elements given at an advanced level. Particular emphasis is placed on the theoretical cases for physical and chemical properties of the elements. Expected Student Learning Activity Weekly Hours for Course* Total Hours for Course (15 week semester) Lecture time (Contact Hours) 2.5 37.5 Reading and Study Time 4 60 Assignments 2 30 Term Credits Earned Examinations 4 (quizzes) 2 (Final Exam) Total Hours 8.5 127.5 3 * Please note that these times are only estimates based on the Department of Education s definition of a credit hour and do not guarantee a specific grade in the course. Students may find that they require more or less time to succeed in the course. Course requirements: Students are expected to attend lectures to develop the necessary background required to evaluate literature sources and to demonstrate this understanding to the class and instructor by way of seminar presentations and written examinations/term papers. Learner Goals: Each learner goal below will be evaluated on quizzes and the final examination and demonstrated on assignments except number 22 which will be evaluated as part of the term paper. Additional learner goals will also be assessed from the term paper submitted but the exact goals will depend on the topic chosen.

2 Upon completion of the sections of the curricular material students should be able to: 1. Understand the limitations inherent to the basic theories of bonding and periodic trends and demonstrate the knowledge by answering appropriate questions on assignments, quizzes, and examinations. Students will be expected to discuss in an essay answer, the scope of these theories by using appropriate molecules that demonstrate the limitations of Lewis structure, VSEPR, crystal field theory, and Molecular Orbital (MO) theory. 2. Construct molecular orbital diagrams taking into account the π-bonding effects in transition metal compounds. Students should be able to draw the corresponding energy level diagrams for σ-bonding in transition metal compounds of differing geometry, and then describe the influence of acceptor and donor substituents in terms of energy changes that occur to the diagram. Students should be able to draw inferences to additional trends in the field such as correlation of the effects to the spectrochemical series. 3. Identify the key molecular orbitals responsible for reactivity in compounds and rationalize the product distribution in related chemical reactions. Students will recognize the importance of specific orbitals that guide the majority of reactivity (HOMO, SHOMO, LUMO, SLUMO) and be able to identify these on a molecular orbital diagram. 4. Understand the structure, bonding and reactivity of inorganic compounds at the advanced level and demonstrate the knowledge by describing the use of Crystal Field Theory and MO theory for transition metal compounds for a variety of geometries. 5. Identify names, structures, and electronic configurations of transition metal complexes through the application of nomenclature rules, d-orbital splitting diagrams, and related calculations of crystal field stabilization energy. 6. Understand the use of the spectrochemical series and the correlation with π-bonding effects in transition metal complexes when determining the appropriate spin configuration for a metal-ligand complex and demonstrate the knowledge by determining high spin vs low spin electronic configurations of electrons in d-orbitals and relating this to the position and presence or absence of π-bonding effects of ligands in the spectrochemical series. 7. Identify the presence of Jahn-Teller distortions and application to spectroscopic methods of characterization and demonstrate the knowledge by identifying the specific electronic configurations that give rise to distortions and the effect these have on the relative energies of the electrons in the d-orbitals. 8. Calculate magnetic moments of transition metal complexes and correlate data with electronic configurations and molecular geometry and demonstrate the knowledge by using the ligands attached to the metal to determine the electronic configuration in terms of d-orbital occupation, figure out the number of unpaired electrons, and relate that number of electrons to the magnetic moment of a molecule using the spin-only magnetic moment formula.

3 9. Understand the use of quantum theory to determine term symbols for transition metal compounds by developing appropriate Orgel diagrams or through the use of Tanabe-Sugano diagrams. Students will demonstrate the knowledge by being able to determine term symbol representations for electronic configurations, draw how these will split in the presence of a ligand field, and develop Orgel diagrams for high spin complexes that summarize the results. Students will also demonstrate knowledge of how to determine the appropriate transitions that occur when radiation of UV/visible wavelengths are absorbed by molecules and select appropriately allowed transitions from the diagrams. Tanabe-Sugano diagrams will be provided and student will have to select appropriate transitions for both high-spin and low-spin valence shell electron configurations of complexes. 10. Utilize Orgel diagrams and Tanabe-Sugano diagrams to interpret UV/Visible spectroscopic data for transition metal complexes and demonstrate the knowledge by assigning the specific absorptions in spectral data to transitions between labeled states. 11. Apply the symmetry properties of molecules to the interpretation of multinuclear nuclear magnetic resonance (NMR) spectroscopy and demonstrate the knowledge through interpretation and discussion of spectral data based on equivalence of nuclei in a structure and the use of multinuclear NMR spectroscopy for different nuclei. 12. Understand the basic principles related to catalytic cycles as they pertain to transition metal catalyzed reactions. Students will demonstrate the knowledge by drawing appropriate catalytic cycles and identifying the basic process by name that applies in each step of the mechanistic description. Students should also be able to perform an electron count for intermediate complexes in the cycles to rationalize changes that occur in the oxidation state of the transition metal atoms in each step. 13. Understand the basic principles related to substitution reactions as they pertain to transition metal reactions. Students will demonstrate the knowledge by performing electron counting and interpreting logical product formation. Students will also identify the different types of substitution reactions occurring at the metal center and relate these to graphical data as it pertains to rates of reactions. 14. Review current literature and issues within the field of inorganic chemistry. The primary purpose in this regard will be the development of a knowledge base in the field of study. Students will utilize the background from lecture to interpret, assess, and summarize current literature related to an assigned seminar topic. Students will demonstrate the knowledge in the preparation of the term paper including content analysis, the use of ACS style guidelines for preparing documents, and the use of ChemDraw software where appropriate for the preparation of figures. 15. Demonstrate oral communication skills and an overall understanding of the course curriculum as they apply to the seminar topic. Students are expected to answer questions from the participants in the course and perform evaluations of other student presentations.

4 Course Outline: Week 1: Distribution of assignment 1. Content: Course introduction. Review of online library resources. ChemDraw primer. Review of electron configuration and exchange energies, and periodic trends. Week 2: Week 3: Week 4: Content: Discussion of the basic background pertaining to the structure and bonding in inorganic chemistry with a focus on transition metal complexes. Quantum numbers, Lewis structures, VSEPR, CFT and d-orbital splitting diagrams. (Ch.1; Ch 2; Ch 5; Ch 20; Ch 21) Assignment 1 due. Solutions for assignment 1 posted. Content: Introduction to molecular orbital (MO) theory and review of group theory for the preparation of MO diagrams. (Ch. 4) Quiz 1 (First 1.5 hr) Content: Introduction to transition metal chemistry (oxidation states, ligands, nomenclature, electron counting, isomerism). Bonding in transition metal compounds using CFT and molecular orbital theory. (Ch. 20-24 and handouts) Weeks 5: Distribution of assignment 2. Content: Introduction to transition metal chemistry (oxidation states, ligands, nomenclature, electron counting, isomerism). Bonding in transition metal compounds using CFT and molecular orbital theory. (Ch. 20-24 and handouts) Week 6: Week 7: Week 8: Content: Introduction to transition metal chemistry (oxidation states, ligands, nomenclature, electron counting, isomerism). Interpretation of UV/visible spectra of transition metal compounds. (Ch. 20-24 and handouts) Assignment 2 due. Solutions for assignment 2 posted. Content: Survey of ligands and bonding motifs. Introduction to multinuclear NMR. (Selected from Ch11-19; Sec. 3.10, 3.11; handouts) Quiz 2. (First 1.5 hr) Assignment 3 distributed. Content: Phosphorous ligands (emphasis on multinuclear NMR studies involving 31 P, 19 F, 13 C, 11 B, 1 H nuclei and the characterization of transition metal phosphine compounds). (Selected from Ch11-19; Sec. 3.10, 3.11; handouts) Week 9: No Class Spring Break Week 10: Content: Transition Metal Chemistry: substitution reactions and redox reactions. (Ch. 26, 27 and handouts)

5 Weeks 11: Week 12: Week 13: Week 14: Week 15: Assignment 3 due. Solutions for assignment 3 posted. Content: Introduction to Organometallic Chemistry and catalytic cycles. Special attention to catalyzed borylation reactions and current coupling methodology. (Ch. 27) Quiz 3. (First 1.5 hr) Content: Organometallic Chemistry and catalytic cycles. Special attention to catalyzed borylation reactions and current coupling methodology continued. (Ch. 27) Term paper due. Seminar presentations. Seminar presentations. Modes of Instruction: The course objectives described above will be achieved by: Listening to lectures and presentations using audio visual aids. Participating in classroom discussions related to published research studies. Conducting research, writing papers and assignments. Reading assignments (text, handouts, journal articles). Required Texts: 1. Housecroft, C. E. and Sharpe, A. G. Inorganic Chemistry, 3 rd Edition; Prentice Hall: New York, 2008. (ISBN: 978-0-13-175553-6) or Housecroft, C. E. and Sharpe, A. G. Inorganic Chemistry, 2 nd Edition; Prentice Hall: New York, 2005. (ISBN: 0-13-039913-2) Recommended Texts: 1. Vincent, A. Molecular Symmetry and Group Theory, Second Edition; John Wiley and Sons: New York, 2001. (ISBN 0-471-48939-5) Try www.wiley.com or amazon.com as the text is out of print Instructor References: Textbooks: 1. Douglas, B., McDaniel, D., Alexander, J. Concepts and Models of Inorganic Chemistry, Third Edition; John Wiley and Sons: New York, 1994. (ISBN 0-471-62978-2) 2. Miessler, G. L., Tarr, D. A. Inorganic Chemistry, Second Edition; Prentice-Hall: New York, 1999. (ISBN 0-13-841891-8) 3. Shriver, D. F., Atkins, P. W. Inorganic Chemistry, Third Edition; W. H. Freeman and Company: New York, 1999. (ISBN 0-7167-3624-1)

6 4. Cotton, F. A., Wilkinson, G., Murillo, C. A., Bochmann, M. Advanced Inorganic Chemistry, Sixth Edition; Wiley-Interscience: New York, 1999. (ISBN 0-471-19957-5 and earlier versions) 5. Collman, J. P., Hegedus, L. S., Norton, J. R., Finke, R. G. Principles and Applications of Organotransition Metal Chemistry; University Science Books: California, 1987. (ISBN 0-935702-51-2) 6. Mackay, K. M., Mackay, R. A. Introduction to Modern Inorganic Chemistry, Third Edition; International Textbook Company: London, 1981. (ISBN 0-7002-0278-1) Journals: Selected journal articles will also be used where appropriate. An abbreviated list of pertinent journals is listed below. Title: Organometallics, Inorganic Chemistry, Chemical Reviews, Chemistry of Materials Publisher: The American Chemical Society Title: Journal of Organometallic Chemistry, European Journal of Inorganic Chemistry Publisher: Elsevier Title: Journal of the Chemical Society, Dalton Transactions, Chemical Communications Publisher: The Royal Society of Chemistry Title: Angewantie Chemie, International Edition in English Publisher: Wiley Interscience Student References: Students are expected to consult the aforementioned journals where appropriate. Additional textbooks pertaining to Inorganic Chemistry may be used as additional sources of information. Method of Evaluation: Assignments 25% Assignment 1: course objectives 1-4 Assignment 2: course objectives 5-10 Assignment 3: course objectives 11 13 Best 2 of 3 Quizzes 30% Quiz 1: course objectives 1-4 Quiz 2: course objectives 5-10 Quiz 3: course objectives 11-13 Final Examination 20% Course objectives: 1-13 Term Paper/Presentation 25% Course objectives: 14, 15 ------ 100%

7 Assignments: Assignments will be distributed by the instructor and will involve consultation of texts and current literature. Assignments will be based on application of the material covered during lectures and where appropriate based on current research themes. A total of three assignments will be distributed during the semester. Solutions will be posted the week when assignments are due so no late assignments will be accepted unless accompanied by a doctor s note or other relevant sources. Quizzes: Regular evaluation of progress will be determined through a series of quizzes throughout the semester. The quizzes will be 1.5 hours in duration and will be based on course material consistent with the assignments. The best 2 of 3 quizzes will be used to determine the overall grade out of 30%. Final Examination: A final examination consisting of 40 multiple-choice questions will be held on TBA. The questions will be commensurate with material deemed by the instructor to be suitable for the comprehensive examination and is cumulative. The examination will not be returned to the student! Term Paper/Presentations: Term papers should be approximately 10 type written pages in length. Diagrams should be prepared in a suitable format (ChemDraw ) and not photocopied. Reproductions are acceptable if they involve pictures or diagrams not suitable for reproduction by common computer programs but must be properly referenced (see below). Complete references should be presented in an appropriate ACS format and copies of literature references MUST be submitted with the paper. The final paper is due on TBA. The term papers topics are to be selected from the current literature and approved by the instructor. Only one student is allowed per topic. The objective is to have the student gain an appropriate level of understanding for the selected topic to be able to describe the general principles governing this area (approx. 5 pages) and then focus in on representative current examples in the literature (approx. 1-2 pages per journal article). We may introduce some of these topics briefly in class and the student is expected to expand on this. In writing the term paper you should address key aspects. Define the topic-what class(es) of compounds are you referring to? What are the structure and bonding considerations? What is the unique feature for this class of compounds? How are these compounds synthesized? How are these compounds characterized? (Are examples of spectra, experimental synthetic details, available through online supplementary materials for the journal article?) How do these compounds react? Attention should also be drawn to theory we have discussed in class and how it pertains to the topic where applicable. For example, are there any distinguishing or unique features in the multinuclear NMR spectra or other methods of characterization? How are the compounds named? What applications are these compounds used for? What are the defining characteristics such as oxidation state, 18-electron count, shape, point group and pertinent IR/Raman data etc. for the transition metal complexes?

8 Textbooks and review articles are excellent sources for background material but do not merely summarize these reference sources. You must search the literature for up to date examples pertaining to your topic. The term paper will account for 15% and the presentation of the term paper content will account for 10% of the overall 25% assigned to the final grade. The presentation will require proper use of ACS styles for citations, document preparation, etc., and also appropriate use of ChemDraw software. Students should consult the evaluation sheet at the end of the syllabus for specific categories that will be evaluated. Seminar presentations will be held in class (unless otherwise stated) and should be 20 minutes in duration (15 min. presentation, 5 min. for questions). Attendance for all seminar presentations is mandatory since students will also be required to assess the other presentations. Each presentation should begin with general background information on structure, bonding, synthesis, etc. as described above and how it pertains to at least one of the recent examples found in the chemistry literature. You should also address why the article you have selected advances that field of study. What warranted the publication and what is unique about the study performed? It is required that you prepare a 2-3-page summary with appropriate references for the class (I will make photocopies in the chemistry office prior to class). Do not read off the slides/overheads you have prepared. This is not an acceptable seminar format. Be prepared to lecture to the class, slides should be a summary of the main points but not the entire presentation. A Powerpoint format is strongly recommended and students should notify the instructor two weeks prior to their presentation so that the appropriate resources can be made available. Some topics are more current than others are! It may be difficult to find current references in some cases. These topics can be discussed by presenting known examples from older literature sources with my prior approval. Sample Referencing Styles Journals: There are several acceptable formats however the student should choose one style and use it consistently. The usual order for citing a journal article is: author, journal, year, volume, page number with the appropriate formatting (bold, italics) indicated below. E.g. Irvine, G. J.; Lesley, M. J. G.; Marder, T. B.; Norman, N. C.; Rice, C. R.; Robins, E. G.; Roper, W.; Whittell, G. R. Chem. Rev. 1998, 98, 2685 2722. Books: The format for reporting a book that has been cited follows the order: authors (usually reported if the book is a collection of papers from different authors), title, editors, publisher, publisher location, year of publication, page number (usually if a particular author in the book has been cited). E.g. Molecular Electronic Devices; Carter, F. L., Ed.; Marcel Dekker: New York, 1982. E.g. Lesley, G.; Yuan, Z.; Stringer, G.; Jobe, I. R.; Taylor, N. J.; Koch, L.; Scott, K.; Marder, T. B.; Williams, I. D.; Kurtz, S. K. In Organic Materials for Nonlinear Optics II, Hahn, R. A.; Bloor, D.; Eds.; R. Soc. Chem. Spec. Publ.: Cambridge, 1991, Vol. 91, pp. 197 203.

9 Letter Grade Scale: The actual grade will be based on the grading scale given below with possible adjustment for class average at the end of the semester (at the instructor's discretion). A+ (100-96) B+ (85-82) C+ (73-70) D+ (61-58) F <50 A (95-91) B (81-78) C (69-66) D (57-54) A- (90-86) B- (77-74) C- (65-62) D- (53-50) Accommodating Students With Disabilities: Dear Students, Southern Connecticut State University provides reasonable accommodations, in accordance with the Americans with Disabilities Act and section 504 of the Rehabilitation Act, for students with documented disabilities on an individualized and flexible basis. If you are a student with a documented disability, the University s Disability Resource Center (DRC) determines appropriate accommodations through consultation with the student. Before you may receive accommodations in this class, you will need to make an appointment with the Disability Resource Center, located in EN C-105A. To speak with me about your approved accommodations or other concerns, such as medical emergencies or arrangements in case the building must be evacuated, please make an appointment as soon as possible.

10 Chemistry 532 Prof. Gerry Lesley Seminar Title: Please comment on the following in terms of the presentations given in class. Where appropriate give a numerical assessment between 0 (poor) and 10 (excellent). 1. How well do you feel the basic principles governing this topic were described? 2. Was the topic discussed in relation to material covered in the lecture portion of the class i.e. were the structure, bonding, synthesis, reactivity, and characterization described (where appropriate)? 3. What was the most interesting or unique feature of the material presented? 4. Did the presenter adequately describe the importance of the journal article that was selected in terms of how it contributed to the advancement in the field of study? 5. What is your opinion of the seminar presentation in terms of: Clarity (0-10) Organization (0-10) Comprehension (0-10) Overall presentation quality (0-10) Additional comments may be included on the back of this page.