Ab Initio and Semi-Empirical Calculations of Cyanoligated Rhodium Dimer Complexs

Author

Yazeed Asiri, East Tennessee State UniversityFollow

Degree Name

MS (Master of Science)

Program

Chemistry

Date of Award

5-2017

Committee Chair or Co-Chairs

Scott Kirkby

Committee Members

Marina Roginskaya, David Close

Abstract

Molecular modeling, using both ab initio and semi-empirical methods has been undertaken for a series of dirhodium complexes in order to improve the understanding of the nature of the chemical bonding in this class of homogeneous catalysts. These complexes, with carboxylamidate and carboxylate ligands, are extremely functional metal catalysts used in the synthesis of pharmaceuticals and agrochemicals. The X-ray crystallography shows anomalies in the bond angles that have potential impact on understanding the catalysis. To resolve these issues, minimum energy structures of several examples (e.g. Rh₂(NHCOCH₃)₄, Rh₂(NHCOCH₃)₄NC, Rh₂(CO₂CH₃)₄, Rh₂(CO₂CH₃)₄NC, Rh₂(CHO₂)₄, and Rh₂(CHO₂)₄NC) were calculated using Hatree-Fock and Density Functional Theory/B3LYP with the LANL2DZ ECP (Rh), and cc-pVDZ (all other atoms) basis sets.

Document Type

Thesis - unrestricted

Recommended Citation

Asiri, Yazeed, "Ab Initio and Semi-Empirical Calculations of Cyanoligated Rhodium Dimer Complexs" (2017). Electronic Theses and Dissertations. Paper 3177. https://dc.etsu.edu/etd/3177

Copyright

Copyright by the authors.