Comp. Inorganic Chemistry


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Computational Inorganic Chemistry

Course description:

This course will explore the fundations and use of (ab-initio quantum chemical) computational methods as applied to inorganic systems.

Topics covered include:

  • introduce generally used quantum chemical methods (HF/DFT/correlated methods) with enough mathematical detail to appreciate the method
  • describe basis sets, their nomenculture, accuracy and common usage
  • a general aim of this course is to provide a broad sense of understanding so that the theoretical component of a combined synthetic/theoretical paper can be understood and the quality of the work assessed
  • develop an understanding of potential energy surfaces, how they are explored, and represented, and what relationship they bare to a reaction path.
  • describe the physical properties that can be calculated, and how such calculations can help in interpreting spectra or analysing mechanisms.
  • develop an understand how molecular orbitals and population analysis can be used as an aid for interpreting chemical bonding and reactivity.

Format:

This course is run in a tutorial format, this means "lectures" will constitute a discussion of the notes and case studies provided online. important Preperation for each "lecture" is essential.

Need some help!

The recommended text for this course:

Introduction to Computational Chemistry, by Frank Jensen, John Wiley and Sons

Other suggested sources of optional reading for this course:
  • Why Chemical Reactions Happen, by J. Keeler and P. Wothers
  • Molecular Quantum Mechanics, by J. P. Atkins and R. Friedman
  • Quantum Chemistry, by Ira N. Levene
  • Modern Quantum Chemistry: Introduction to Advanced Electronic Structure Theory, by A. Szabo and N. Ostlund

Contact Me

I'm very happy to revceive questions via e-mail:

Introduction to the Schrodinger Equation

  1. Notes: pdf
  2. Links to the full paper for the examples mentioned in the notes.
    • doi:10.1021/om060717g
      Organolanthanide-Catalyzed Hydroamination/Cyclization Reactions of Aminoalkynes. , A. Motta, I.L. Fragala, and T.J. Marks, Organometallics, 2006, 25, 5533
    • doi: 10.1021/ic701814h
      Synthesis, Characterization, and DFT/TD-DFT Calculations of Highly Phosphorescent Blue Light-Emitting Anionic Iridium Complexes. , D. Di Censo, S. Fantacci, F. De Angelis, C. Klein, N. Evans, K. Kalyanasundaram, H.J. Bolink, M. Gratzel, and M.K. Nazeeruddin Inorganic Chemistry, 2008, 47(3), 980
    • doi: 10.1002/chem.200600103
      Characterising the Electronic Structure of Ionic Liquids; An examination of the 1-Butyl-3-Methylimidazolium Chloride Ion Pair, P. Hunt, B. Kirchner and T. Welton, Chem. Eur. J, 2006, Vol 12, Iss 26, 6762-6775

The Wavefuntion

  1. Notes: pdf updated for 2013
  2. Resources
    • look through some of the basis sets available at the Basis Set Exchange
    • what basis sets are available in Gaussian, a common computational chemsitry code G09
    • look at some of the pesudo-potentials available from the Stuttgart group
  3. Case Study: Exploring the PES and catalytic reactions using computational chemistry; Migratory NO Insertion followed byPH3 Addition:
    • notes: pdf
    • doi: 10.1021/ja961995h
      "Theoretical Studies of Inorganic and Organometallic Reaction Mechanisms. 11. Migratory Insertion of Coordinated Nitric Oxide into Cobalt-Carbon Bonds" S. Niu and M. Hall, J Am. Chem. Soc., 1997, 119, 3077
    • doi: 10.1021/jp961558p
      "Comparison of Hartree-Fock, Density Functional, Moller-Plesset Perturbation, Coupled Cluster, and Configuration Interaction Methods for the Migratory Insertion of Nitric Oxide into a Cobalt-Carbon Bond" S. Niu and M. Hall, J Phys. Chem. A. 1997, 101, 1360

The potential energy surface or PES

  1. Notes: pdf updated for 2013
  2. Case Study: A closer look at hydroamination using Lanthanide Catalysts
    • doi:10.1021/om060717g
      Organolanthanide-Catalyzed Hydroamination/Cyclization Reactions of Aminoalkynes. , A. Motta, I.L. Fragala, and T.J. Marks, Organometallics, 2006, 25, 5533

Methods, an introduction to HF and DFT

  1. Notes: pdf updated for 2013

Properties

  1. Notes: pdf
  2. Case Study: The Si-Si triple bond
    • doi: 10.1021/om058033g
      Ab Initio and DFT Study of the 29Si NMR Chemical Shifts in RSitSiR , M. Karni, Y. Apeloig, N. Takagi, and S. Nagase, Organometallics, 2005, Vol 24, p6319
    • doi: 10.1021/ja065817s
      Solid-State 29Si NMR Study of RSiSiR: A Tool for Analyzing the Nature of the Si-Si Bond , V. Kravechenko, R. Kinjo, A. Sekiguchi, M. Ichinohe, R. West, Y. Balazs, A. Schmidt, M. Karni and Y.Apeloig. JACS, 2006, Vol 128, p14472

Bonding

  1. Notes: pdf
  2. Case studies
    • doi: 10.1002/chem.200600103
      Characterising the Electronic Structure of Ionic Liquids; An examination of the 1-Butyl-3-Methylimidazolium Chloride Ion Pair, P. Hunt, B. Kirchner and T. Welton, Chem. Eur. J, 2006, Vol 12, Iss 26, 6762-6775

Bonding Case Studies

  1. Notes: pdf
  2. Case studies
    • Understanding the TM-Si bond
      doi: 10.1021/om970580h
      "Examination of Metal-Silicon Bonding through Structural and Theoretical Studies of an Isostructural Set of Five-Coordinate Silyl Complexes, Os(SiR3)Cl(CO)(PPh3)2 (R ) F, Cl, OH, Me)" K Hčbler, P. Hunt, S. Maddock, C. Rickard, W Roper, D. Salter, P. Schwerdtfeger, and L. Wright, Organometallics, 1997, Vol 16, p5076
    • Dewar-Chatt-Duncanson model of bonding
      doi: 10.1002/1521-3749(200105)627:5<985::AID-ZAAC985>3.0.CO;2-#
      "Theoretical Studies of Organometallic Compounds. Ligand Site Preference in Iron Tetracarbonyl Complexes Fe(CO)4L" Y. Chen, M. Hartmann, G. Frenking, Z. Anorg. Allg. Chem., 2001, Vol 627, p985
      The doi link does not work for this journal so here is a link to the right journal page, (scroll down) to find the paper
    • Theoretical insight into Lewis acidity
      doi: 10.1021/ic034141o
      "Why Is BCl3 a Stronger Lewis Acid with Respect to Strong Bases than BF3?" F. Bessac and G. Frenking, Inorg. Chem., 2003, Vol 42, p7990

Additional Case Studies (from other years)

  1. Combining computational chemistry with property evaluations: A complex NMR based investigation into an unusual bonding mode
    • notes: pdf
    • doi: 10.1021/ja047665b
      "Unusual Ar-H/Rh-H JHH NMR Coupling in Complexes of Rhodium(III): Experimental Evidence and Theoretical Support for an η1-Arene Structure" J. Krumper, M. Gerisch, A. Magistrato, U. Rothlisberger, R. Bergman and T. Don Tilley JACS 2004, Vol 126, p12492
    • doi: 10.1002/mrc.1447
      "Reliable NMR chemical shifts for molecules in solution by methods rooted in density functional theory" C. Benzi, O. Crescenzi, M. Pavone and V. Baron, Magn. Reson. Chem. 2004, Vol 42, S57
  2. Zigler-Natta Ni based catalytic cycle for olefin polyermerisation
    • notes: pdf
    • doi: 10.1021/om049545i
      "Use of Computational and Synthetic Chemistry in Catalyst Design: A New Family of High-Activity Ethylene Polymerization Catalysts Based on Titanium Tris(amino)phosphinimide Complexes" C. Beddie, E. Hollink, P. Wei, J. Gauld, and D. Stephan, Organometallics, 2004, Vol 23, p4240