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Modeling Organorhodium Catalysis

Bayden, Alexander S (2006) Modeling Organorhodium Catalysis. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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The first project considered in this dissertation was the improvement of an existing global optimization algorithm that uses extended dimensionality to find global minima of Lennard-Jones clusters. The speed of this algorithm was increased by three orders of magnitude, primarily by improving the algorithm for compressing the system from 4D to 3D at constant energy. The second project was modeling the adsorption of H2 molecules on the Si(100) surface using density functional theory (DFT) with the PW91 functional. Consistent with the experiments, the calculations predicted an energetic preference for clustering of occupied sites in a dimer row. However, our calculations did not verify the unbuckling induced by H2 adsorption reported by Buehler and Boland. The third project was modeling molybdenum and rhodium-catalyzed [2 + 2 + 1] cycloisomerization reaction using DFT with the B3LYP functional. We found that in the rhodium-catalyzed [2 + 2 + 1] cycloisomerization reactions of allenes the oxidative addition step determined both the rate and the product of the reaction. For the molybdenum-catalyzed reaction the rate was controlled not by oxidative addition, but by the next step, the attachment of a carbon monoxide molecule from the media to the molybdenum atom. The fourth project was modeling the transfer of hydrogen from one side of the heterocyclic ring to another in rhodium(I) catalyzed allenic Pauson-Khand type reactions. Our calculations showed that this process occurs after the cyclization step. We have also discovered a novel mechanism for this process - hydride transfer; however, we believe that in most cases the reaction proceeds by beta-hydride elimination.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Bayden, Alexander Sabayden@pitt.eduABAYDEN
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairJordan, Kenneth Djordan@pitt.eduJORDAN
Committee MemberSchafmeister, Christian Emeister@pitt.eduMEISTER
Committee MemberZuckerman, Daniel Mdmz@ccbb.pitt.eduDDMMZZ
Committee MemberBrummond, Kay Mkbrummon@pitt.eduKBRUMMON
Date: 16 March 2006
Date Type: Completion
Defense Date: 28 November 2005
Approval Date: 16 March 2006
Submission Date: 4 November 2005
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Institution: University of Pittsburgh
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Degree: PhD - Doctor of Philosophy
Thesis Type: Doctoral Dissertation
Refereed: Yes
Uncontrolled Keywords: 4D; beta-hydride elimination; DFT; extended dimensionality; global minima; H2; hydride transfer; Lennard-Jones clusters; modeling; molybdenum; Pauson-Khand; rhodium; Si(100); [2 + 2 + 1] cycloisomerization
Other ID:, etd-11042005-145318
Date Deposited: 10 Nov 2011 20:04
Last Modified: 15 Nov 2016 13:51


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