M. Sc. Syllabus Semester – 2

CH-411: Inorganic Reaction Mechanism and Organometallics

Reaction Mechanism: Substitution in octahedral and square planar complexes; lability, trans-effect, Conjugate base mechanism, racemisation, Electron Transfer.

Reactions: inner sphere and outer sphere mechanism, Marcus theory.

Inorganic photochemistry: Photosubstitution and photoredox reactions of chromium, cobalt and ruthenium compounds, Adamson’s rules.

Lanthanides and Actinides: Spectral and Magnetic Properties, NMR Shift reagents.

Organometallic Chemistry: 18- electron rule, metal carbonyls, nitrosyls, cabonyl hydrides, isolobal analogy, dioxygen and dinitrogen compounds. Metal alkyls, carbenes, carbynes, alkenes, alkynes, and allyl complexes. Hydrides, Metallocenes, Metal arene complexes. Carbonylate anions, agostic interaction, Oxidative addition and reductive elimination, insertion and elimination reactions. Homogeneous and heterogeneous catalysis. Fluxional molecules. Metal-Metal bonding and Metal clusters.

Text Books:

  1. Inorganic Chemistry: Principles of Structure and Reactivity by J. E. Huheey, E. A. Keiter and R. L. Keiter, 4th Ed. Harper Collins 1993.
  2. Concepts and Models of Inorganic Chemistry by B. E. Douglas, D. H. McDaniel, J. J. Alexander, John Wiley, 1993, 3rd Ed.

References:

  1. Reaction Mechanism in Inorganic Chemistry by R. R. Jordan Oxford Univ. Press, 1998. 2nd Ed.
  2. Advanced Inorganic Chemistry by F. A. Cotton and G. W. Wilkinson, JohnWiley & Sons, 1988, 5th Ed.
  3. Organometallics by Ch. Elschenbroich, A. Salzer, VCH, 1995, 2nd Ed.
  4. Organotransition Metal Chemistry: Fundamental Concepts and Applications by A. Yamamoto, John Wiley 1986.
  5. Organometallic Chemistry of the Transition Metals by R. H. Crabtree, John Wiley, 1993, 2nd Ed.
  6. Inorganic Chemistry by D. F. Shriver and P. W. Atkins, 3rd Ed., Oxford.

CH-421: Organic Reactions and Mechanisms

Aliphatic Nucleophilic Substitution: The SN2, S¬N1, mixed S¬N1 and SN2 and SET mechanisms. The neighbouring group mechanism. Classical and nonclassical carbocations, phenonium ions, norbornyl system, common carbocation rearrangements. The SNi mechanism. Nucleophilic substitution at an allylic, aliphatic trigonal and a vinyl carbon. Reactivity effects of substrate structure, attaching nucleophile, leaving group and reaction medium.

Electrophilic Substitution: Aliphatic: Bimolecular mechanisms: SE1, SE2 and SEi. The SE1 mechanism, electrophilic substitution accompanied by double bond shifts. Effect of substrates, leaving group and the solvent polarity on the reactivity.

Aromatic: The arenium ion mechanism, orientation and reactivity, energy profile diagrams. The ortho/para ratio, ipso attack, orientation in other ring systems. Quantitative treatment of reactivity in substrates and electrophiles.

Aromatic Nucleophile Substitution: The SNAr, SN1, benzyne and SRN1 mechanisms. Reactivity; effect of substrate structure, leaving group and attacking nucleophile.

Free Radical Reactions: Types of free radical reactions, free radical substitution mechanism, mechanism at an aromatic substrate, neighbouring group assistance. Reactivity for aliphatic and aromatic substrates at a bridgehead. Reactivity in the attaching radicals. The effect of solvents on reactivity.

Addition to Carbon-Carbon Multiple Bonds: Mechanistic and stereochemical aspects of addition reactions involving electrophiles, nucleophiles and free radicals, regio- and chemo-selectivity, orientation and reactivity. Addition to cyclopropane ring. Hydroboration.

Addition to Carbon-Hetero Multiple Bonds: Mechanism of metal hydride reduction of saturated and unsaturated carbonyl compounds, acids, esters and nitriles. Addition of Grignard reagents, organozinc and organolithium reagents to carbonyl and unsaturated carbonyl compounds.

Elimination Reactions: The E2, E1 and E1cB mechanisms and their spectrum. Orientation of the double bond. Reactivity; effects
of substrate structures, attaching base, the leaving group and the medium.

Text Books:

  1. Advanced Organic Chemistry by J. March, John Wiley & Sons, 1992
  2. Organic Chemistry by S. H. Pine, McGraw Hill, 1987.

Reference:

  1. Modern Synthetic Reactions by H. O. House, W.A. Benjamin, Inc., 1972
  2. Understanding Organic Reaction Mechanism by A. Jacobs, Cambridge 1998.
  3. Organic Chemistry by J. M. Hornback, Books Coley, 1998.
  4. Organic Chemistry by P.Y. Bruice, Prentice Hall, 1998.
  5. Organic Reaction and their Mechanism by P.S. Kalsi, New Age, 1996.

CH – 425: Organic Chemistry Laboratory

Separation techniques and characterization (t.l.c, column, distillation, crystallization, GC etc.)
Organic synthesis: Representative reaction to be covered Esterfication and saponification, Oxidation, Reduction, Nucleophilic substitution,
Cycloaddition reactions, Grignard reaction, Condensation reactions, Preparation of dyes, Aromatic electrophilic substitution, Heterocyclic synthesis, Solidphase synthesis, Natural product extraction: Solasidine, Caffeine, Nicotine, Peptine, Rosine, Carotenoids, Computational methods of retro-synthetic analysis modeling and calculation.

Text Books:

  1. Vogel’s Text Book of Practical Organic Chemistry, by Brian S. Furniss, ELBS Longman, 5th edition, 1996.
  2. Techniques and Experiments for Organic Chemistry, by Addison Ault, University Science Book, 6th Edition.
  3. Instrumental techniques for Analytical Chemistry by Frank Settle, Printice Hall, 1997.

CH-432: Chemical Dynamics and Electrochemistry

Chemical Dynamics: Methods of determining rate laws, collision theory of reaction rates, steric factor, Arrhenius equation and activated complex theory, kinetic and thermodynamic control of reactions, ionic reactions, kinetic salt effects, steady state kinetics, unimolecular reactions and their treatments (LindemannHinshelwood and Rice-Ramsperger-Kassel-Marcus [RRKM] theory), Complex reactions (chain reactions, and oscillatory reactions), photochemical reactions, homogeneous catalysis, enzyme kinetics, studies of fast reactions by flow method, relaxation method, flash photolysis and NMR. Dynamics of molecular reactions, probing the transition state, dynamics of barrierless chemical reactions in solution, dynamics of unimolecular reactions.

Electrochemistry: Electrochemical cells, Nernst equation and applications of Debye-Huckel-theory, Electrolytic conductivity and the Debye-Hückel-Onsangar treatment, electrified interfaces, overpotential, corrosion.

Text Books:

  1. Chemical Kinetics by Keith Laidler, Harper and Row, 1995.
  2. Chemical Kinetics: The study of reaction rates in solution by Kenneth A. Connors, VCH, 1990
  3. Electrochemistry by Carl H. Hamann, Andrew Hamnett and Wolf Vielstich, Wiley VCH, 1998.

References:

  1. Reaction Kinetics by M. J. Pilling and P. W. Seakins, Oxford Press, 1997
  2. Modern Electrochemistry 1. Volume 1 and 2, by J. O’M. Bockris and A. K. N. Reddy, Kluwer Academic, 2000.
  3. Electrochemical Methods, by A. J. Bard and L. R. Faulkner, John Willey, 1980

CH-433: Applications of Spectroscopy

Vibrational: Symmetry and shapes of AB2, AB3, AB4, AB5 and AB6, modes of bonding in ambidentate ligands, application of resonance Raman spectroscopy particularly for the study of active sites of metalloproteins.

Electron Spin Resonance: Hyperfine coupling, spin polarization for atoms and transition metal ions, spin-orbit coupling and significance of g-tensor, application of transition metal complexes having one unpaired electron including biological systems and to inorganic free radicals such as PH4, F2– and [BH3]–.
Nuclear Magnetic Resonance: The contact and pseudo contact shifts, factors affecting nuclear relaxation, some applications including biological systems, an overview of NMR of metal nuclides. Chemical shift, spin-spin interaction, shielding mechanism, complex spin-spin interaction, virtual coupling stereochemistry, hindered rotation, Karplus curve, variation of coupling constant with dihedral angle, nuclear magnetic double resonance, simplification of complex spectra, shift reagent, spin tickling, nuclear overhauser effect (NOE), resonance of other nuclei.

13C NMR: Chemical shift, 13C coupling constants, two-dimensional NMR spectroscopy, NOISY, DEPT, INEPT terminology.

Mössbauer: Basic principles, spectral parameters and spectrum display. Application to the studies of (1) bonding and structures of Fe2+ and Fe3+ compounds including those of intermediate spin, (2) Sn2+ and Sn4+ compounds – nature of M-L bond, coordination number, structure and (3) detection of oxidation state and inequivalent MB atoms.

Electrochemical techniques: CV, polarography, coulometry, amperometry.

Thermal Methods: TGA, DSC and DTA.

UV-Vis: Woodward rule for conjugated dienes and carbonyl compounds.

IR: Characteristic vibrational frequencies of different functional groups, effect of hydrogen bonding and solvent effect on vibrational frequencies, overtones, combination and Fermi resonance bands.

Mass: Instrumentation, Mass spectral fragmentation of organic compounds, McLafferty rearrangement, examples of mass spectral fragmentation of organic compounds with respect to their structure determination.

ORD & CD: Definition, deduction of absolute configuration, octant rule for ketones.

Data Analysis: Uncertainties, errors, mean, standard deviation, least square fit, testing the fit (C2 test, residual etc.). Signal to noise ratio.

Text Books:

  1. Physical Methods in Chemistry by R. S. Drago, Saunders, 1992
  2. Inorganic Electronic Spectroscopy by A. B. P. Lever, Elsevier, 1984, 2nd Ed.
  3. Spectrometric Identifications of Organic Compounds by R. M. Silverstein, John Wiley, 1991.
  4. Introduction to Spectroscopy by D.L. Pavia, G. M. Lampman, G. S. Kriz, Harcourt College Publisher, NY, 2001

References:

  1. Organic Spectroscopy by William Kemp, ELBS 3rd Ed. 1994.