CH3201 : Chemistry of Transition Elements (Spring 2013)

Details of CH3201 (Spring 2013)

Level: 3

Type: Theory

Credits: 3.0

Course Code	Course Name	Instructor(s)
CH3201	Chemistry of Transition Elements	Sumit Khanra

Syllabus
Bonding in Coordination Compounds: Term Symbols & microstates (d2 electronic configuration), R-S coupling. Drawbacks of Crystal field theory & emergence of Ligand Field Theory (LFT); Nephelauxetic effect & ratio. Molecular Orbital Theory (MOT): MO theory of Transition Metal complexes in Octahedral, Tetrahedral & Square Planar Geometric arrangements; Effect of pi-bonding in MO theory. Concept of Metal-Metal Bonding in cluster compounds; quadruple bond in [Re2Cl8]2- cluster; quintuple bond. Coordination Chemistry & Spectra: Electronic spectroscopy of Transition Metal Complexes; Ligand Field Spectra; Ligand Field Splitting; Interelectronic Repulsion Parameter(B); Orgel Diagrams; Tanabe-Sugano Diagrams; Tetragonal Distortions from Octahedral Symmetry & Jahn-Teller Theorem. Selection Rules of Electronic Transition: Laportes Forbidden Rule; Spin Selection Rule Charge Transfer Spectra (CT): Ligand to Metal Charge Transfer (LMCT); Metal to Ligand Charge Transfer (MLCT); Ligand to Ligand Charge Transfer (LLCT) Molecular Magnetism in Coordination Chemistry: Free Atoms & Ions: Spin Coupling, Orbital Coupling, Spin-Orbit Coupling, Russell-Saunders or LS Coupling. Van-Vlecks formula for susceptibility, Strength of Ligand Fields: Weak Field Case & Strong Field Case, Term Splitting & Electronic Configuration. Spin Orbit Coupling on A, E & T Terms. Measurements: Gouy Method, Faraday Methods & Superconducting Quantum Interface Device (SQUID) magnetometer. Mononuclear Systems with Metal ions of the First Transition Series; Exchange Coupled Dinuclear and Trinuclear Compounds, Spin Hamiltonian parameters, Heisenberg-Dirac-Van Vleck (HDVV) Hamiltonian, Spin Frustration. Orthogonality of magnetic orbitals; Ferromagnetic & Antiferromagnetic exchange interactions; EPR spectroscopy: Basic Principles, Selection Rules, representation of EPR spectrum, First derivative spectrum, Hyperfine & Superhyperfine interactions, determination of hyperfine coupling constant, Relaxation mechanism, Isotropic, Axial & Rhombic spectra, g-value and factors affecting the values. EPR spectroscopy of paramagnetic mononuclear & polynuclear compounds: distortion in the coordination environment & origin of anisotropic systems like axial & rhombic spectra. Reaction Kinetics and Mechanism in Transition Metal Chemistry: Lability &Inertness, Thermodynamic & Kinetic Stability Substitution reactions in Square Planar Complexes; Rate law for Nucleophilic Substitution in a Square Planar Complexes: Associative, Interexchange associate, Dissociative, Interexchange Dissociative Laws; Trans Effect; Reaction Mechanism Kinetics & Mechanism of Octahedral Substitution Reactions; Influence of Acid & Base in Rates Mechanism of Redox Reactions; Electron Transfer Reactions; Outer Sphere Mechanism; Inner Sphere Mechanism. Recent advances in catalysis involving transition metal compounds

Syllabus

Bonding in Coordination Compounds: Term Symbols & microstates (d2 electronic configuration), R-S coupling. Drawbacks of Crystal field theory & emergence of Ligand Field Theory (LFT); Nephelauxetic effect & ratio. Molecular Orbital Theory (MOT): MO theory of Transition Metal complexes in Octahedral, Tetrahedral & Square Planar Geometric arrangements; Effect of pi-bonding in MO theory. Concept of Metal-Metal Bonding in cluster compounds; quadruple bond in [Re2Cl8]2- cluster; quintuple bond.

Coordination Chemistry & Spectra: Electronic spectroscopy of Transition Metal Complexes; Ligand Field Spectra; Ligand Field Splitting; Interelectronic Repulsion Parameter(B); Orgel Diagrams; Tanabe-Sugano Diagrams; Tetragonal Distortions from Octahedral Symmetry & Jahn-Teller Theorem. Selection Rules of Electronic Transition: Laportes Forbidden Rule; Spin Selection Rule Charge Transfer Spectra (CT): Ligand to Metal Charge Transfer (LMCT); Metal to Ligand Charge Transfer (MLCT); Ligand to Ligand Charge Transfer (LLCT)

Molecular Magnetism in Coordination Chemistry: Free Atoms & Ions: Spin Coupling, Orbital Coupling, Spin-Orbit Coupling, Russell-Saunders or LS Coupling. Van-Vlecks formula for susceptibility, Strength of Ligand Fields: Weak Field Case & Strong Field Case, Term Splitting & Electronic Configuration. Spin Orbit Coupling on A, E & T Terms. Measurements: Gouy Method, Faraday Methods & Superconducting Quantum Interface Device (SQUID) magnetometer.
Mononuclear Systems with Metal ions of the First Transition Series; Exchange Coupled Dinuclear and Trinuclear Compounds, Spin Hamiltonian parameters, Heisenberg-Dirac-Van Vleck (HDVV) Hamiltonian, Spin Frustration. Orthogonality of magnetic orbitals; Ferromagnetic & Antiferromagnetic exchange interactions;
EPR spectroscopy: Basic Principles, Selection Rules, representation of EPR spectrum, First derivative spectrum, Hyperfine & Superhyperfine interactions, determination of hyperfine coupling constant, Relaxation mechanism, Isotropic, Axial & Rhombic spectra, g-value and factors affecting the values. EPR spectroscopy of paramagnetic mononuclear & polynuclear compounds: distortion in the coordination environment & origin of anisotropic systems like axial & rhombic spectra.

Reaction Kinetics and Mechanism in Transition Metal Chemistry: Lability &Inertness, Thermodynamic & Kinetic Stability Substitution reactions in Square Planar Complexes; Rate law for Nucleophilic Substitution in a Square Planar Complexes: Associative, Interexchange associate, Dissociative, Interexchange Dissociative Laws; Trans Effect; Reaction Mechanism
Kinetics & Mechanism of Octahedral Substitution Reactions; Influence of Acid & Base in Rates
Mechanism of Redox Reactions; Electron Transfer Reactions; Outer Sphere Mechanism; Inner Sphere Mechanism. Recent advances in catalysis involving transition metal compounds

References
1. J. E. Huhee, R. L. Keiter and E. A. Keiter, Inorganic Chemistry, Harper Collins, New York (1993) 2. W. L. Jolly, Modern Inorganic Chemistry, Macgraw-Hill, New York (1991) 3. F. A. Cotton, G. Wilkinson, C. A. Murillo and M. Bochmann, Advanced Inorganic Chemistry: 6th Ed., John Willey Chichester (1999) 4. D. F. Shriver and P. W. Atkins, Inorganic Chemistry, Oxford University Press, Oxford (1999) 5. G. Wulfsberg, Inorganic Chemistry, University Science Books (2000) 6. O. Kahn, Molecular Magnetism, VCH: New York, (1993) 7. L. Que. Jr., Physical Methods in Bioinorganic Chemistry, University Science Books(2000) 8. E. A. V. Ebsworth, D. W. H. Rankin and S. Cradock, Structural Methods in Inorganic Chemistry, Blackwell, Oxford (1987) 9. F. Basolo and R. G. Pearson, Mechanism of Inorganic Reactions: A study of Metal Complexes in Solution, John Wiley, New York (1958) 10. Magnetochemistry by R L Dutta & Shyamal

References

1. J. E. Huhee, R. L. Keiter and E. A. Keiter, Inorganic Chemistry, Harper Collins, New York (1993)
2. W. L. Jolly, Modern Inorganic Chemistry, Macgraw-Hill, New York (1991)
3. F. A. Cotton, G. Wilkinson, C. A. Murillo and M. Bochmann, Advanced Inorganic Chemistry: 6th Ed., John Willey Chichester (1999)
4. D. F. Shriver and P. W. Atkins, Inorganic Chemistry, Oxford University Press, Oxford (1999)
5. G. Wulfsberg, Inorganic Chemistry, University Science Books (2000)
6. O. Kahn, Molecular Magnetism, VCH: New York, (1993)
7. L. Que. Jr., Physical Methods in Bioinorganic Chemistry, University Science Books(2000)
8. E. A. V. Ebsworth, D. W. H. Rankin and S. Cradock, Structural Methods in Inorganic Chemistry, Blackwell, Oxford (1987)
9. F. Basolo and R. G. Pearson, Mechanism of Inorganic Reactions: A study of Metal Complexes in Solution, John Wiley, New York (1958)
10. Magnetochemistry by R L Dutta & Shyamal

Course Credit Options

Sl. No.	Programme	Semester No	Course Choice
1	IP	2	Core
2	IP	4	Not Allowed
3	MS	6	Core
4	RS	1	Elective

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Details of CH3201 (Spring 2013)

Course Credit Options