Dissertation committee:
Επικ. Καθηγητής κ. Ν. Ψαρουδάκης, (επιβλέπων), Ομότιμος Καθηγητής κ. Κ. Μερτής, Εντεταλμένος Ερευνητής Ε.Ι.Ε. κ. Ε. Σημαντήρας
Summary:
In this thesis we study, with the help of Density Functional Theory
computation, the protonation reaction of the unbridged quadruple metal-metal
bond of [Mo2Cl8]4- anion producing the bridged triply bonded hydride [Mo2(μ-
H)(μ-Cl)2Cl6]3-.
The reactant, product, intermediates and transition states are located on the
potential energy surface. The calculations are made in both the absence and
presence of solvent.
Full reaction profiles are calculated and compared to the relevant experimental
data. In this way, the mechanism of the reaction is elucidated. This involves
two steps.
At the first step, which is the rate determining step, we have a proton
transfer from an oxonium ion to the quadruple bond. The second involves the
internal rearrangement of chlorine atoms which is much faster, compared to the
first step.
Activation energies with a mean value of 19 kcal/mol are calculated, in
excellent agreement with experimental values.
Keywords:
Density functional theory, Molybdenum complexes, Clusters, Protonation, Reaction mechanism
