STUDIES OF SOLUTION STRUCTURE AND ITS CHEMICAL REACTIVITY BY MOLECULAR SPECTROSCOPY
Abstract
Solution structure of NaCo(CO)(,4) in 1,2 DME, THF and THP has been studied by infrared spectroscopic technique. The NaCo(CO)(,4) salt exists in form of two, three and five kinds of anion sites in 1,2 DME, THF and THP respectively. Several Types of ion site modifiers such as C211, C221, C222, H(,2)O, NaB(C(,6)H(,5))(,4) and (BzlPh(,3))PCo(CO)(,4), each with different effectiveness, were used for ion site conversion to help in sorting out the individual solution structurite. The anion sites found in those solutions are--site I, solvent separated ion pair and free ion; site II, contact ion pair; site III, triple ions with two anions; site IV, triple ions with two cations and site V, close ion pair. The reactivity of different kinds of anion sites for the NaCo(CO)(,4) salt toward a particular chemical reaction is not the same. We find that, only the anion sites that have a direct Na...O(TBOND)C- contact will undergo a reaction with (CH(,3))(,3)SnCl. Conversion of part of the contact ion sites into the non contact ion sites slows down the reaction while the complete conversion stops the reaction altogether. The use of dual symmetry in describing the CO stretching vibrations of (C(,6)H(,5))(,3)SnCo(CO)(,4) was discussed. This compound has a C(,3v) geometry at the -Co(CO)(,4) but its modes of vibration in the solution are represented by a C(,3v)/T(,d) dual symmetry not the conventional C(,3v) symmetry. High quality Raman spectra of (C(,6)H(,5))(,3)SnCo(CO)(,4) in MTHF were used to prove this argument.
Degree
Ph.D.
Subject Area
Chemistry
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