Computational chemistry of organometallic and inorganic species

QD Chemistry

Davin, Thomas J. ; McGrady, John E.

University:University of Glasgow

Department:School of Chemistry

关键词: computational chemistry, hydrogenase, hydrogen addition, theoretical studies, phosphorus cluster, calculated NMR parameters, calculated chemical shift, calculated coupling constant, structural rearrangement;   

Others  :  http://theses.gla.ac.uk/925/1/2009davin1phd.pdf

来源: University of Glasgow

【 摘 要 】

This thesis presents computational investigations of problems relatedto redox processes and structural rearrangement in inorganic systems.Density functional theory has been used to gain insight into the originand nature of such reactions. The work presented concerns two maintopics: hydrogenase-like systems containing an Fe2 core and carbonphosphoruscluster compounds. In chapters II and III, we describe theimpact of reduction, an important phenomenon in the H2 productioncatalytic cycle, on a hydrogenase-like model. In collaboration withTalarmin and co-workers who have conducted careful electrochemicalstudies, we have used DFT to identify structures of species observedin cyclic voltammetry. We have also studied the binding of a protonto similar systems and, through the calculation of chemical shifts andcoupling constants, confirmed the structures of iron hydrides observedby 1H NMR spectroscopy. In chapter V we focus on carbon-phosphorussystems that can exist in 2 or more isomeric forms. We address firstthe case of a system of formula C6H4P3 which has the right valenceconfiguration to exist either as a planar structure or as a 3-dimensionalcluster (nido according to Wade’s rules). We then examine whetherit is possible to control the preferred conformation by the addition ofsubstituents on the phenyl ring. Finally, we look at the rearrangementof a planar diphosphene into a cage isomer and try to understandthe mechanism and in particular the role of the protonation in theconversion from planar to 3-dimensional structure.