Dft Study of Titanium Cubane and Molybdenum Sulphide Compounds.

Identifier:  TDX:860

Handle:  https://hdl.handle.net/20.500.11797/TDX860

Authors:  Gracia Budria, José Manuel

Abstract:
The overall framework of this report aims to summarize the work we have done over the past four years. Conceptually, this thesis is divided into three parts. The nucleus is based on a joint project with prof. Mena, of the University of Alcalá, whose group is involved in the synthesis and characterization of new aza- and oxo- titanium cubanes. These families of compounds are basically obtained from preorganized titanium tridentate ligands which can incorporate almost all the metals of the periodic table and yield the corresponding heterometallic cubanes. In this respect, the theoretical study is based on and adapted from the progress in the laboratory work. Practically every section in this part starts by describing the experimental data available for the specific system studied when we began the analysis. Then we go on to describe the theoretical study and attempt to involve the reader in the problems discussed. As a consequence of the advance in the experimental work, NMR spectra are used to characterize the new compounds. This leads us to initiate studies in the computational simulation of NMR chemical shifts. The most theoretical part of this report is an assimilation of these studies. The excellent results obtained for the cubane compounds enabled us to extend the knowledge acquired to other interesting fields and our group has started a study of the NMR shielding tensors in polyoxometalate compounds. The third part of the thesis focuses on some molybdenum-sulphide clusters and their activity as catalysts.Chapters 3 and 4 focuse on the electronic structure of the new titanium cubane compounds recently synthesized by Mena et al. We work parallel to an experimental group to compare and contrast the theoretical and experimental data, and so establish the base chemistry