CHM 609: Transition Metal Organometallic Chemistry
Course content:
Structure and bonding: Brief overview of transition metal orbitals, electron counting, formal oxidation state, 18-e rule and its exceptions, isoelectronic and isolobal analogies, common geometries for transition metal complexes (Crystal Field Theory, MO description), σ- and π-bonding, types of ligands and their properties, soft vs hard ligands.
Reactions of organometallic complexes: ligand substitution/ exchange/dissociation processes and thermochemical considerations, catalyzed and assisted ligand substitution reactions, oxidative addition (definition, mechanism, thermodynamic consideration), oxidative addition of non-polar and polar electrophilic reagents, reductive elimination (bite angle effects, π-acid effects), transmetallation (definition, mechanism, utility), insertion/de-insertion, nucleophilic and electrophilic attack on coordinated ligands.
Complexes with classic Lewis base donors: Amines, phosphines and other related donors.
Complexes with metal-carbon σ-bonds: (a) Metal carbonyl complexes: Synthesis, structure and bonding; IR spectroscopy; Reactions; Related complexes with cyanide, nitrosyl, and dinitrogen ligands. (b) Metal alkyl complexes: Synthesis, stability and structure; Reactions; Activation of C-H bonds. (c) Alkylidene and alkylidyne complexes: Synthesis; structure and bonding; Reactivity; Olefin metathesis.
Metal-element multiple-bonded complexes: Oxo, sulfido, imido, hydroazido, nitrido- complexes: Synthesis, bonding, structure, spectroscopy, and reactivity.
Complexes with metal-metal multiple bonds: Synthesis, structure and bonding, spectroscopic and magnetic properties, and reactions.
Metal complexes of π-ligands: (a) Alkene complexes: Synthesis; Bonding; Reactivity. (b) Alkyne complexes: Synthesis; Bonding; Reactivity. (c) Cyclopentadienyl complexes: Discovery of ‘sandwich’ complexes; Bonding; Properties of Cp complexes of 3d metals; Substituted metallocenes; Zigler-Natta polymerization; Half-sandwich complexes. (d) Allyl and dienyl complexes: Synthesis; Structure and properties; Reactivity. (e) Arene complexes: Bis-arene complexes; Arene half-sandwich complexes; η2 to η4 coordinated arenes; Seven and eight-membered ring ligands.
Modern applications of organometallic chemistry: (a) Small molecule activation and functionalization: mechanistic and practical view. (b) Organometallic materials.
Suggested Reading:
• Crabtree, R. H. The Organometallic Chemistry of the Transition Metals, 3rd Ed.; Wiley-Interscience: New York, 2001.
• Hartwig, J. F. Organotransition Metal Chemistry From Bonding to Catalysis, 1st Ed.; University Science Books: Sausalito, CA, 2010.
• Collman, J.P.; Hegedus, L.S.; Norton, J.R.; Finke, R.G. Principles and Applications of Organotransition Metal Chemistry; University Science: Mill Valley, CA, 1987.
• Spessard, G.O.; Miessler, G.L. Organometallic Chemistry. Prentice Hall: Upper Saddle River, NJ, 1996.
• Huheey, J.E.; Keiter, E.A.; Keiter, R.L. Inorganic Chemistry: Principles of Structure and Reactivity, 4th Ed.; HarperCollins: New York, 1993.
• Jordan, R. B. Reaction Mechanisms of Inorganic and Organometallic Systems;2nd Ed.; Oxford University Press: Oxford, 1998.
• (a) Bochmann, M. Organometallics 1; Oxford University Press: New York, 1994. (b) Bochmann, M. Organometallics 2; Oxford University Press: New York, 1994.
• Elschenbroich, C.; Salzer, A. Organometallics: A Concise Introduction, 2nd Ed.; VCH: New York, 1992.
• Shriver, D. F.; Atkins, P. W. Inorganic Chemistry, 3rd Ed.; W. H. Freeman: New York, 1999.
• Attwood, J. D. Inorganic and Organometallic Reaction Mechanisms, 2nd Ed.; VCH Publishers Inc.: New York, 1997.
• Nugent, W. A.; Mayer, J. A. Metal-Ligand Multiple Bonds, 1st Ed.; Wiley-Interscience, 1987.
• Elschenbroich, C. Organometallics, 3rd, Completely Revised and Extended Edition;Wiley-VCH Verlag GbmH & Co. KGaA, Weinheim, Germany, 2006.
• Cotton, F. A.; Murillo, C. A.; Walton, R. A. Multiple Bonds between Metal Atoms, 3rd Ed.; Springer Science Inc. New York, 2005.
CHM 401: Non-Transition Metal Chemistry
Course content:
Concepts and principles of nontransition metal chemistry: An overview of bonding models in inorganic chemistry, Chemical forces, Bent’s rule, Application of molecular orbital theory to polyatomic molecules (localized and delocalized orbitals), Walsh diagrams, Fluxional molecules, Atomic inversion, Berry pseudorotation, Inert Pair Effect, The role of p- and d- orbital participation in nonmetals, Periodicity, periodic anomalies of the nonmetals, multiple bonding in heavier main group elements, charge transfer complexes.
Representative chemistry (structure and bonding) and applications of of s- and p-block elements: alkali metals (electrides), boranes, carboranes, boron clusters, Wade’s rules, metallacarboranes, boron nitride nanotubes, fullerenes, graphene, CNT, organosilicon compounds, silicates and aluminosilicates, zeolites, silylenes and R3Si+, Polysilanes, stability and activation of dinitrogen, phosphorus oxides, oxyacids, phosphines, anion chemistry of N, P, As and Sb, singlet and triplet oxygen, oxygen activation, chemistry of chalcogens, polychalcogenides, sulfur-nitrogen compounds, halogens, pseudohalogens, interhalogens, noble gases, CFC.
Chemistry of carbenes, push-pull carbenes, stable heavier carbene analogues (Silicon, Germanium, Tin and lead): synthesis, characterisation and reactivity.
Multiple bonding in heavier main-group elements: Synthesis, structure and reactivity.
Main group organometallic chemistry: Preparation, stability aspects and reactions. Structurally diverse π-cyclopentadienyl complexes of the main group elements. Element-Element Addition to Alkynes (Si-Si, Ge-Ge, B-B, S-S, Se-Se, Ge-Sn, Si-B, Sn-B, S-B, Se-P, Si-S).
Interlocked macromolecules: catenanes, rotaxanes, pseudorotaxanes.
Suggested Reading:
• Inorganic Chemistry-Principles of Structure and Reactivity. J. E. Huheey, E. A. Keiter, R. L. Keiter, 4th Edn. Harper-Collins, NY, 1993.
• Chemistry of the Elements. N. N. Greenwood, and Earnshaw, A. 1st Edn. Pergamon, Oxford, 1989.
• Concepts and Models of Inorganic Chemistry. B. Douglas, D. McDaniel, J. Alexander, 3rd Edn. John Wiley, New York. 1993.
• Advanced Inorganic Chemistry. F. A. Cotton, G. Wilkinson, C. A. Murillo, M. Bochmann, 3rd Edn. John Wiley and Sons Press, 1995.
• Modern Inorganic Chemistry. W. L. Jolly, 2nd Edn. McGraw-Hill, NY, 1991.
• Inorganic Chemistry. D. F. Shriver, and P. W. Atkins. 3rd Edn. Oxford University, Oxford, 1999.
CHM 302: Chemistry of Transition Metals
Course content:
Coordination Chemistry: Coordination number and stereochemistry of coordination complexes (coordination number 2-9). Electronic configurations and states, the group state and energy levels, free-ion term, Symmetry orbitals and bonding in transition-metals complexes: L-S coupling for dn states, splitting of one electron levels in an octahedral and tetrahedral environment, Orgel and Tanabe-Sugano diagrams, Charge-Transfer bands, Jahn-Teller distortion. Applications of CFSE, Stereochemistry of non-rigid and fluxional molecules. Thermodynamic aspects of coordination complexes, Nephelauxetic effect, Irving William series, Factors affecting ligand field stabilization energies, First row transition elements, heavy transition elements, M-M bonded complexes, C-H activation, agostic interactions, ortho-metallation. Kinetic aspects: reaction and aquation rates, electron transfer reactions. Reaction mechanism in inorganic reactions. Redox reactions, Trans effect.
Chemistry of Lanthanides and Actinides: Electronic configuration, colour and magnetism, properties of lanthanides and actinides. Synthesis of trans-Uranic elements, chemistry of uranium compounds.
Organometallic chemistry: 18e rule and its exceptions, isolobal and isoelectronic analogies. s and π bonding, types of ligands, soft vs hard ligands. Structure, bonding and reactivity studies of metal carbonyls, nitrosyls, dinitrogen complexes. Homogeneous and heterogeneous catalysis, oxidative addition, reductive elimination reactions, organometallic complexes with metal-metal bonds.
Molecular Magnetism: Paramagnetism, Diamagnetism and Ferromagnetism, Neel and Curie Temperature, Magnetic Susceptibility.
Inorganic Chemistry of Biological Systems: Essential and trace elements in biological systems, energy sources for life, metalloporphyrins, dioxygen binding, transport, and utilization.
Suggested Reading:
• Inorganic Chemistry-Principles of Structure and Reactivity. J. E. Huheey, E. A. Keiter, R. L. Keiter, 4th Edn. Harper-Collins, NY, 1993.
• Chemistry of the Elements. N. N. Greenwood, and Earnshaw, A. 1st Edn. Pergamon, Oxford, 1989.
• Concepts and Models of Inorganic Chemistry. B. Douglas, D. McDaniel, J. Alexander, 3rd Edn. John Wiley, New York, 1993.
• Advanced Inorganic Chemistry. F. A. Cotton, G. Wilkinson, C. A. Murillo, M. Bochmann, 3rd Edn. John Wiley and Sons Press, 1995.
• Modern Inorganic Chemistry. W. L. Jolly, 2nd Edn. McGraw-Hill, NY, 1991.
• Inorganic Chemistry. D. F. Shriver, and P. W. Atkins. 3rd Edn. Oxford University, Oxford, 1999.
• Theoretical Inorganic Chemistry, M. C. Day, 2nd Edition, East-West Press, India, 2007.
• Essential Trends in Inorganic Chemistry, D. M. P. Mingos, OUP, New York 2010.
• Inorganic Chemistry, G.Wulfsberg, Viva Books P. Ltd, India, 2010.
• Advanced Structural Inorganic Chemistry, W.-K. Li, G.-D. Zhou,T. C. W. Mak, IUCr Monograph, OUP, New York, 2008.
CHM 102: Basic Inorganic Chemistry
Course content:
Concepts and principles of non transition metal chemistry: An overview of bonding models in inorganic chemistry, Chemical forces, Bent’s rule, Application of molecular orbital theory to polyatomic molecules (localized and delocalized orbitals), Walsh diagrams.
Main group Chemistry: General characteristics of s- and p-block elements [hydrides, oxides, halides], comparative study of second short period elements (B to F) with heavy congeners (Al to Cl). Electron deficient molecules, hyper-valency, concept of multi-centered bonding.
Oxidation and Reduction: The central role of transfer of electrons in chemical processes. The importance of splitting of water. Redox chemistry of extraction (Ellingham diagrams). Conversion of chemical energy into electricity. Batteries and modern state of solid state batteries, Fuel cells.
Transition metal complexes: types of ligands and stereochemistry of complexes. Preliminary idea about crystal field theory [CFT] (splitting of d-orbital energy levels for Oh, Td and square planar complexes), application of CFT to explain color and magnetism of transition metal complexes. Concept of 18 electron rule among transition metal complexes. Preliminary ideas about relationship of transition metal complexes and metalloenzymes.
Radioactivity and Nuclear Chemistry: The nature of radioactive radiations, detection and measurements. Theory of disintegration, disintegration series. Half-life and average life period, artificial radioactivity, applications. Nuclear fission, nuclear fusion, critical mass.
Analytical Chemistry: Errors in Chemical Analysis, Precision and Accuracy, Mean, Median, Range, deviations, and errors. Principal of Gravimetric and volumetric Principals, classification of chromatographic techniques, paper chromatography, TLC, Column chromatography.
Suggested Reading:
• Inorganic Chemistry, Shriver and Atkins, Fourth Edition, Oxford University Press, 2006.
• Concise Inorganic Chemistry, J. D. Lee, Fifth Edition, Blackwell Publishing, 2006.
• Basic Inorganic Chemistry, F. A. Cotton, G. Wilkinson, P. L. Gaus, Third Edition, John Wiley and Sons Press, 1995.
• Concepts and Models of Inorganic Chemistry, B. Douglas, D. McDaniel, J. Alexander, Wiley India (P.) Ltd., India, 2010.