Main Group Chemistry and Molecular Magnetism

CY5019 : Organometallic Chemistry CY5019 : Organometallic Chemistry

Course Objectives: The learners should be able to analyze the mechanism of selected catalytic organic reactions from the structure-bonding aspects and reactivity of simple organometallic compounds
Learning Outcomes: At the end of the course, the learners should be able to
Identify the structure and bonding aspects of simple organometallic compounds
Apply different electron counting rules to predict the shape/geometry of low and high nuclearity metal carbonyl clusters
Identify the different types of organometallic reactions and apply the above concepts to explain different catalytic reactions

Course Contents:

Organometallic chemistry of d-block elements: 18-electron rule, concept of hapticity; synthesis, structure and bonding of homo and heteroleptic metal-carbonyls, nitrosyls, alkyls, alkenes, allyl, alkynes, and arenes. Synthesis and reactivity of Fischer and Schrock carbenes.
Infrared spectra of metal carbonyls and olefins.
Neutral spectator ligands: phosphines and N-heterocyclic carbenes.
Metal clusters, Low and high nuclearity clusters, clusters having interstitial atoms, electron counting schemes:
polyhedral skeletal electron pair theory/Mingo’s rule.
Structure and Isolobal analogies.
Metallocenes and bent-metallocenes.
Fluxionality and dynamics in organometallic chemistry
Reactions of organometallic complexes: Substitution, oxidative addition, reductive elimination, insertion and deinsertion.
Catalysis: Organometallic catalysts, Terminology in catalysis: Turnover, turnover number (TON), turnover frequency (TOF). Hydrogenation, Hydroformylation, Monsanto process, Wacker process, Ziegler-Natta polymerization, C-C coupling reactions, Olefin Metathesis and metathesis polymerization
Organometallic compounds of s-block elements: Organo-lithium, beryllium and magnesium compounds

Text Books:

M. Weller, T. Overton, J. Rourke and F. Armstrong, Inorganic Chemistry, 6th Edition, Oxford University Press, 2014. (South Asia Edition 2015)
E. Huheey, E. A. Keiter, R.L. Keiter and O. K. Mehdi, Inorganic Chemistry, Principles of Structure and Reactivity, 4th Edition, Pearson, 2006.
D. Gupta and A. J. Elias; Basic Organometallic Chemistry: Concepts, Synthesis, and Applications, 2nd Edition, Universities Press (India), 2013.
N. Greenwood and A. Earnshaw, Chemistry of the Elements, 2nd Edition, Elsevier, 1997.
P Powell, Principles of organometallic Chemistry, 2nd Edition, Springer, 2009.

CY5012 : Main Group Chemistry and spectroscopic characterization of Inorganic Compounds CY5012 : Main Group Chemistry and spectroscopic characterization of Inorganic Compounds

Course Objectives: The learners should be able to apply, analyze and evaluate the structure and bonding aspects of inorganic and organometallic compounds derived from main group elements, using spectroscopic techniques.
Learning Outcomes: At the end of the course, the learners should be able to:
Identify the basic principles related to structure and bonding of s & p block elements
Use various spectroscopic principles to characterize inorganic and organometallic compounds
Predict the synthesis and bonding properties of s and p block elements

Course Contents:

Structure and bonding in polyhedral boranes and carboranes, styx notation; Wade’s rule; electron count in polyhedral boranes; synthesis of polyhedral boranes; isolobal analogy; boron halides; phosphine-boranes; borazine. Organyls of Al, Ga, In and Tl.
Silanes, silicon halides, silicates, silanols; germanium, tin and lead organyls; phosphorous halides, acids and oxyacids, phosphazenes; sulphur halides, oxo acids of sulphur; structural features and reactivity of reactivity of S-N heterocycles; chemistry of halogens and group 18 elements.
Structural elucidation using the following spectroscopic techniques.
Symmetry and Point group analysis of simple inorganic compounds.
Electronic spectroscopy: electronic transitions in inorganic and organometallic compounds.
Infrared and Raman spectroscopy of simple inorganic molecules; predicting number of active modes of vibrations, analysis of representative spectra of metal complexes with various functional groups.
Applications of 1H and 13C NMR in inorganic and organometallic chemistry, fluxionality and dynamics; deriving activation and thermodynamic parameters; NMR spectral analyses of B, Al, Si, F and P containing compounds. Elementary aspects of Electron paramagnetic resonance (EPR) spectroscopy of inorganic compounds – g-values, hyperfine and super hyperfine coupling constants; selected applications in inorganic chemistry.
Mass spectrometry, basic principles, ionization techniques, isotope abundance, molecular ion; illustrative examples from supramolecules, inorganic/coordination and organometallic compounds.

Text Books:

Weller, T. Overton, J. Rourke and F. Armstrong, Inorganic Chemistry, 6th Edition, Oxford University Press, 2014. (South Asia Edition 2015)
E. Huheey, E. A. Keiter, R.L. Keiter and O. K. Mehdi, Inorganic Chemistry, Principles of Structure and Reactivity, 4th Edition, Pearson, 2006.
A. Cotton, G. Wilkinson, C. A. Murillo and M. Bochmann, Advanced Inorganic Chemistry, 6th Edition, Wiley, 2007.

Abragam and B. Bleaney, Electron Paramagnetic Resonance of Transition Ions, Oxford University Press, 1970. (Reprint Edition 2013)
S. Drago, Physical Methods for Chemists, 2nd Edition,Saunders, 1992.
N. Banwell and E. M. McCash, Fundamentals of Molecular Spectroscopy, 4th Edition, McGraw-Hill, 1994.
Gunther, NMR Spectroscopy, Basic Principles, Concepts and Applications in Chemistry, 3rd Edition, Wiley VCH, 2013.
A. Cotton, Chemical Applications of Group Theory, Wiley, 3rd Edition, 1990. (Paperback 2008).

CY6011 : Solid State Chemistry CY6011 : Solid State Chemistry

Course Objectives: To identify and apply the concepts involved in the syntheses, structure and physical properties of crystalline inorganic solids
Learning Outcomes: At the end of the course, the learners should be able to:
Arrive at the chemical compositions based on unit cell contents and fractional coordinates. Index cubic powder XRD pattern, determine unit cell parameter and lattice type
Index non-cubic powder XRD patterns based on unit cell parameters provided Calculate densities from powder XRD data Identify and apply suitable strategies for synthesizing inorganic crystalline solids in polycrystalline and single crystal forms Correlate and Predict structure-composition-properties (magnetic, electrical and optical) in inorganic crystalline solids

Course Contents:

Crystal Structure: Crystalline and amorphous solids; One and two dimensional lattices, crystal systems, Bravais lattices, point groups: α-Po, fcc, bcc and hcp metals and their packing efficiency, ionic radii ratios; structure types of ionic solids: CsCl, NaCl, ZnS, Na2O, CaF2, CdCl2, NiAs, ZnO, CdI2, Cs2O, PbO, TiO2, ReO3, perovskite ABO3, YBa2Cu3O7, K2NiF4, Ag2HgI4, spinel and olivine. Polyhedral structure description of solid state compounds. Frenkel and Schotky defects, colour centers, Crystallographic shear (CS) in WO3-x
Powder x-ray diffraction, indexing the powder XRD patterns, Systematic absences, Structure factor, determination of lattice type, unit cell parameter and density for α-Po, fcc, bcc and hcp metals, NaCl, ZnS, diamond, CuZn, CuAu, AuCu3 and other simple compounds. Neutron diffraction.
Preparative methods: Solid state reaction, chemical precursor method, co-precipitation, sol-gel, metathesis, self-propagating high temperature synthesis, ion-exchange reactions, intercalation / deintercalation reactions; hydrothermal and template synthesis; High pressure synthesis.
Methods of Single Crystal Growth: Solution growth; Melt Growth-Bridgeman, Czochralski, Kyropoulus, Verneuil; Chemical Vapour Transport; Fused Salt Electrolysis; Hydrothermal method; Flux Growth.
Electrical properties: Band theory of solids -metals and their properties; semiconductors – extrinsic and intrinsic, Hall effect; thermoelectric effects (Thomson, Peltier and Seebeck); insulators – dielectric, ferroelectric, pyroelectric and piezoelectric properties, multiferroics.
Superconductivity: Basics, discovery and high Tc materials.
Magnetic properties: Dia, para, ferro, ferri, and antiferro magnetic types; soft and hard magnetic materials; select magnetic materials such as spinels, garnets and perovskites, hexaferrites and lanthanide-transition metal compounds; magnetoresistance.
Thermal analysis: TGA, DTA, DSC

Text Books:

R. West, Solid State Chemistry and its Applications, John Wiley & Sons, 1984. (Reprint Edition)
E. Smart and E. A. Moore, Solid State Chemistry – An Introduction, 4th Edition, CRC Press, 2012.
V. Keer, Principles of the Solid State, 2nd Edition, New Age International, 2017.
Weller, T. Overton, J. Rourke, and F. Armstrong, Inorganic Chemistry, 6th Edition, Oxford University Press, 2014. (South Asia Edition 2015)

CY6103 : Chemistry of Crystalline Inorganic Solid state Materials CY6103 : Chemistry of Crystalline Inorganic Solid state Materials

Synthesis, structure, properties, structure-property correlations and potential applications of crystalline inorganic solid state materials.
Superconductors – (Ba,K)BiO3, Cuprates, LnFeAsO, MgB2, CaC6
CMR materials – La1-xSrxMnO3
Ferroic compounds – BaTiO3, PbTiO3, Bi4Ti3O12, SrRuO3
Photoluminescent materials – Lanthanide compounds Porous materials – zeolites, AlPO, MeAlPO, SAPO.
Organic-inorganic hybrid materials – Ruddlesden-Popper (RNH3)2An-1MX3n+1 metal halides, MOF compounds
Ionic Conductors – NASICON, AgI, NaAl11O17
Thermoelectric materials – NaxCoO2, AgSbTe2, CoSb3, Y14MnSb11
Compounds for intercalation and redox reactions – LiCoO2, LiVS2, NASICON, Chevrel phases
Other relevant examples from recent literature

Text Books:
Rao, C.N.R.; Gopalakrishnan, J. New directions in Solid State Chemistry; Cambridge University Press: Cambridge, 1997 (ISBN 0-521-49907-0). Cheetham, A.K. Solid state chemistry: compounds; Oxford University Press: Oxford, 1992 (ISBN: 0198551665, 9780198551669). Lalena, J.N.; Cleary, D.A. Principles of Inorganic Materials Design ; Wiley: New York, 2010 (ISBN: 978-0-470-40403-4). Maier, J. Physical Chemistry of Ionic Materials: Ions and Electrons in Solids; Wiley: New York, 2004 (ISBN: 978-0-470-87076-1). Solid-state Chemistry of Inorganic Materials VI (SYMPOSIUM QQ AT THE 2006 MRS FALL MEETING); Curran Associates, Inc., 2007 (ISBN: 1558997962).

CY1001 : Chemistry CY1001 : Chemistry

Chemical Thermodynamics
Second Law of Thermodynamics – Entropy change accompanying various processes (isothermal expansion, phase transition, heating, entropy of mixing of perfect gases); Absolute entropy and the Third Law of Thermodynamics; Statistical entropy; Spontaneity of a chemical reaction and Gibbs energy; Standard Gibbs energies of formation and reactions; Thermodynamic functions (A, G, U & H) and four fundamental equations, Maxwell relationships; variation of G with T and P, Gibbs-Helmholtz equation, Chemical potential; G versus extent of reaction ( ), Equilibrium constant through chemical potential (gas equilibria), relation between Kp & Kc; Phase equilibria, Gibbs phase rule, phase diagrams of water and carbon dioxide (supercritical H2O & CO2), Clausius-Clapeyron equation; Liquid-solid phase diagrams – two-component eutectic systems and cooling curves.

Chemical Kinetics
Parallel, opposing and consecutive reactions; Mechanism of complex chemical reactions; Analysing mechanisms using the steady-state approximation, Chain reactions (hydrogen-bromine reaction); Unimolecular reactions (Lindemann-Hinshelwood approach); Transition State Theory for bimolecular reactions (thermodynamic approach); Enzyme catalysis (Michaelis-Menten Mechanism). Chemisorption and Langmuir Isotherm.

Basic Concepts of Quantum Chemistry

Uncertainty principle; Motion of a quantum mechanical particle in one dimension; The Schr�dinger wave equation for the hydrogen atom; physical meaning of a wave function, radial wave functions and probability densities, quantum numbers, wave functions and orbital shapes.

Transition metal chemistry

Bonding in transition metal complexes; coordination compounds; crystal field theory, octahedral, tetrahedral and square planar complexes; CFSE; Jahn-Teller theorem; Spectral, electronic and magnetic properties of coordination complexes..

Organometallic chemistry

Synthesis structure and reactivity of metal carbonyls; 16 and 18 electron rules ; Variety of ligands and hapticity; Type of reactions: Oxidative addition, Reductive elimination, Migratory insertion; Homogeneous catalysis, Hydrogenation, Hydroformylation, Monsanto process, Wacker process.

Aromaticity

Aromatic, non-aromatic and anti-aromatic compounds. Aromatic nucleophilic substitution reactions.

Pericyclic reactions

Definition, classifications, electrocyclic reaction of butadiene and hexatriene, photochemical [2+2] and thermal [4+2] cycloadditions, Sigmatropic rearrangements – limited to Cope and Claisen rearrangements, FMO approach – Woodward Hoffmann rules and basic stereochemistry aspects of the above reactions.

Text Books:
Atkin’s Physical Chemistry by PW Atkins and J de Paula, 8th and 9th Eds., Oxford University Press. Organic Chemistry by J Clayden, N Greeves and S Warren, 2nd Edition 2012, Oxford University Press. Shriver and Atkin’s Inorganic Chemistry by P Atkins, T Overton J Rourke, M Weller and F Armstrong, 4th Edition 2009, Oxford University Press.