The crystal field splitting parameter, Δ, has been used to correlate a wide range of properties of first-row transition metal complexes. This includes structure, electronic spectra, magnetic properties and some aspects of thermochemistry. It is perhaps the single most useful parameter in understanding coordination chemistry.
This course begins with a review of simple crystal field theory, highlighting both strengths and weaknesses of the model. The model is then extended to the more general ligand field theory and the concept of interelectronic repulsion is introduced followed by a description of Russell-Saunders terms.
Electronic spectra of high-spin octahedral complexes are interpreted using Orgel diagrams and tetrahedral complexes are treated in this way as well. The treatment is then extended to the use of Tanabe-Sugano diagrams, especially to cover the interpretation of the more difficult d2 d7 octahedral cases as well as low-spin complexes.
It is expected that students should be able to interpret ALL simple electronic spectra and predict both position and intensity based on Orgel/Tanabe-Sugano diagrams and the appropriate selection rules and appreciate the relationships between the electron configuration, co-ordination geometry, and spectroscopic properties of transition metal complexes.
Magnetic properties of high-spin octahedral and tetrahedral complexes are simplified in terms of systems having A and E ground terms or T ground terms. It is expected that students should be able to calculate the spin-only magnetic moment for any high-spin complex and predict the nature of any variations found experimentally.
Following this part of the course, the occurrence and extraction of the first-row transition metals is covered. Then an in-depth look at the descriptive chemistry of a few selected metals is highlighted in terms of their oxide and aqua chemistry and halides. The structure of a number of these can be characterised as either cubic or hexagonal close packed arrays with the metal ions fitting in between the layers. The metal ions are invariably octahedral, regardless of the stoichiometry of the salt.
Some simple coordination complexes such as acetates and 2,4-pentanedione (acac) complexes of these selected metal ions will be covered as well.An introduction to inorganic reaction mechanisms, a subject that has rapidly grown in importance during the last thirty years, will be presented to you. This introduction is necessarily short (5 lectures) and selective, since the course is primarily concerned with coordination compounds of first row transition metal ions. The primary objective of this part of the course is to make you familiar with the following topics:
A short course (4 lectures) on organometallic chemistry involving only transition metals will then be presented. Again, organometallic chemistry has developed enormously during the last 40 years. Currently approximately half of the world's research publications in chemistry relate to organometallic compounds. Over and above, organometallics play a vital role in the economy of the developed nations. The aim of the course is to introduce to you:
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