Computational Studies of Coordinatively Unsaturated Transition Metal Complexes

PDF Version Also Available for Download.

Description

In this research the validity of various computational techniques has been determined and applied the appropriate techniques to investigate and propose a good catalytic system for C-H bond activation and functionalization. Methane being least reactive and major component of natural gas, its activation and conversion to functionalized products is of great scientific and economic interest in pure and applied chemistry. Thus C-H activation followed by C-C/C-X functionalization became crux of the synthesis. DFT (density functional theory) methods are well suited to determine the thermodynamic as well as kinetic factors of a reaction. The obtained results are helpful to industrial catalysis ... continued below

Creation Information

Vaddadi, Sridhar December 2006.

Context

This dissertation is part of the collection entitled: UNT Theses and Dissertations and was provided by UNT Libraries to Digital Library, a digital repository hosted by the UNT Libraries. It has been viewed 420 times , with 4 in the last month . More information about this dissertation can be viewed below.

Who

People and organizations associated with either the creation of this dissertation or its content.

Chair

Committee Members

Publisher

Rights Holder

For guidance see Citations, Rights, Re-Use.

  • Vaddadi, Sridhar

Provided By

UNT Libraries

With locations on the Denton campus of the University of North Texas and one in Dallas, UNT Libraries serves the school and the community by providing access to physical and online collections; The Portal to Texas History and UNT Digital Libraries; academic research, and much, much more.

Contact Us

What

Descriptive information to help identify this dissertation. Follow the links below to find similar items on the Digital Library.

Degree Information

Description

In this research the validity of various computational techniques has been determined and applied the appropriate techniques to investigate and propose a good catalytic system for C-H bond activation and functionalization. Methane being least reactive and major component of natural gas, its activation and conversion to functionalized products is of great scientific and economic interest in pure and applied chemistry. Thus C-H activation followed by C-C/C-X functionalization became crux of the synthesis. DFT (density functional theory) methods are well suited to determine the thermodynamic as well as kinetic factors of a reaction. The obtained results are helpful to industrial catalysis and experimental chemistry with additional information: since C-X (X = halogens) bond cleavage is important in many metal catalyzed organic syntheses, the results obtained in this research helps in determining the selectivity (kinetic or thermodynamic) advantage. When C-P bond activation is considered, results from chapter 3 indicated that C-X activation barrier is lower than C-H activation barrier. The results obtained from DFT calculations not only gave a good support to the experimental results and verified the experimentally demonstrated Ni-atom transfer mechanism from Ni=E (E = CH2, NH, PH) activating complex to ethylene to form three-membered ring products but also validated the application of late transition metal complexes in respective process. Results obtained supported the argument that increase in metal coordination and electronic spin state increases catalytic activity of FeIII-imido complexes. These results not only encouraged the fact that DFT and multi-layer ONIOM methods are good to determine geometry and thermodynamics of meta-stable chemical complexes, but also gave a great support to spectroscopic calculations like NMR and Mossbauer calculations.

Language

Identifier

Unique identifying numbers for this dissertation in the Digital Library or other systems.

Collections

This dissertation is part of the following collection of related materials.

UNT Theses and Dissertations

Theses and dissertations represent a wealth of scholarly and artistic content created by masters and doctoral students in the degree-seeking process. Some ETDs in this collection are restricted to use by the UNT community.

What responsibilities do I have when using this dissertation?

When

Dates and time periods associated with this dissertation.

Creation Date

  • December 2006

Added to The UNT Digital Library

  • May 12, 2008, 3:25 p.m.

Description Last Updated

  • Dec. 5, 2013, 11:44 a.m.

Usage Statistics

When was this dissertation last used?

Yesterday: 0
Past 30 days: 4
Total Uses: 420

Interact With This Dissertation

Here are some suggestions for what to do next.

Start Reading

PDF Version Also Available for Download.

Citations, Rights, Re-Use

Vaddadi, Sridhar. Computational Studies of Coordinatively Unsaturated Transition Metal Complexes, dissertation, December 2006; Denton, Texas. (digital.library.unt.edu/ark:/67531/metadc5488/: accessed September 26, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; .