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001 on1144495097;

003 OCoLC;

005 20200326032315.0;

006 m o d ;

007 cr unu||||||||;

008 200313s2019 ncua obm 000 0 eng d;

035 a| (Sirsi) o1144495097;

035 a| (OCoLC)1144495097;

049 a| EREE;

090 a| QD281.A2;

100 1 a| Warden, Elizabeth Fae,e| author.?| UNAUTHORIZED;

245 10 a| Theoretical probe to the mechanism of Pt-catalyzed C-H acylation reaction :b| possible pathways for the key acylation reaction of platinacycles /c| by Elizabeth Fae Warden.;

264 1 a| [Greenville, N.C.] :b| [East Carolina University],c| 2019.;

300 a| 119 pages :b| illustrations (some color);

336 a| textb| txt2| rdacontent;

337 a| computerb| c2| rdamedia;

338 a| online resourceb| cr2| rdacarrier;

347 a| text fileb| PDFc| 8.576 MB2| rda;

538 a| System requirements: Adobe Reader.;

538 a| Mode of access: World Wide Web.;

502 b| M.S.c| East Carolina Universityd| 2019.;

500 a| Presented to the faculty of the Department of Chemistry;

500 a| Advisor: Yumin Li;

500 a| Title from PDF t.p. (viewed March 23, 2020).;

520 3 a| Transition metal-catalyzed C-H bond functionalization offers a variety of desirable transformations of simple hydrocarbons to more complex compounds with applications being applied in pharmaceuticals to material sciences. In 2017, Dr. Huo's research group reported a unique Pt-catalyzed acylation of 2-aryloxypyridines through direct C-H activation. The significance of this reported reaction is represented in the experiment occurring without any oxidants or additives; furthermore, presenting this relatively straight forward reaction mechanism which is initiated only in the presents of platinum. However, through computational analysis the key acylation step of the cyclometalated platinum complex has shown quite intriguing results. Utilization of the nudged elastic band (NEB) method followed by a min-mode optimization of the potential transition states has shown preference towards a nucleophilic substitution over the previously proposed electrophilic addition during the key acylation step. Theoretically, this DFT study at M062X/6-311g**/def2-TZVP-Pt level of theory was unable to simulate the initial formal electrophilic substitution reaction proposed as the arenium ion C could not be minimized. Therefore based on current results the preferred pathway is as follows: (1) nucleophilic substitution of the acyl chloride to form five-coordinate acylplatinum complex with a barrier of 21.7083 k cal/mol (B), followed by (2) 1,2-migration of the acyl group from the platinum to the metalated carbon to form a Pt-arene n-complex or platinacyclopropane with a barrier of 15.0713 kcal/mol (E). Lastly, (3) Re-aromatization of E leads to the acylated product P with a barrier of 35.3138 kcal/mol. Further probing and key mechanistic results will be presented.;

504 a| Includes bibliographical references.;

650 0 a| Acylation.=| ^A1345027;

650 0 a| Activation (Chemistry)=| ^A825614;

650 0 a| Chemical reactions.=| ^A23139;

653 a| Platinum Catalyst;

653 a| C-H Activation;

653 a| Computational Chemistry;

653 a| NEB;

653 a| Theoretical Study;

653 a| Nudged Elastic Band Method;

653 a| Dimer;

653 a| Transition State localization;

653 a| QST2;

653 a| Gaussian;

653 a| C-H Funtionalization;

700 1 a| Li, Yumine| degree supervisor.=| ^A1033392;

710 2 a| East Carolina University.b| Department of Chemistry.?| UNAUTHORIZED;

856 40 z| Access via ScholarShipu| http://hdl.handle.net/10342/7595;

949 o| wjh;

994 a| C0b| ERE;

596 a| 1 4;

998 a| 5266575;

999 a| CLICK ON WEB ADDRESSw| ASISc| 1i| 5266575-1001l| JNETm| JOYNERr| Ys| Yt| JNE3ETDu| 3/13/2020x| ETDz| JERESOURCE;

999 a| CLICK ON WEB ADDRESSw| ASISc| 1i| 5266575-2001l| HSLELECm| HSLr| Ys| Yt| HEETDu| 3/13/2020x| ETDz| HERESOURCE;

Theoretical probe to the mechanism of Pt-catalyzed C-H acylation reaction : possible pathways for the key acylation reaction of platinacycles / by Elizabeth Fae Warden.

Author/creator	Warden, Elizabeth Fae author.
Other author	Li, Yumin degree supervisor.
Other author	East Carolina University. Department of Chemistry.
Format	Theses and dissertations
Publication	[Greenville, N.C.] : [East Carolina University], 2019.
Description	119 pages : illustrations (some color)
Supplemental Content	Access via ScholarShip
Subjects	Acylation. Activation (Chemistry) Chemical reactions.

Summary	Transition metal-catalyzed C-H bond functionalization offers a variety of desirable transformations of simple hydrocarbons to more complex compounds with applications being applied in pharmaceuticals to material sciences. In 2017, Dr. Huo's research group reported a unique Pt-catalyzed acylation of 2-aryloxypyridines through direct C-H activation. The significance of this reported reaction is represented in the experiment occurring without any oxidants or additives; furthermore, presenting this relatively straight forward reaction mechanism which is initiated only in the presents of platinum. However, through computational analysis the key acylation step of the cyclometalated platinum complex has shown quite intriguing results. Utilization of the nudged elastic band (NEB) method followed by a min-mode optimization of the potential transition states has shown preference towards a nucleophilic substitution over the previously proposed electrophilic addition during the key acylation step. Theoretically, this DFT study at M062X/6-311g**/def2-TZVP-Pt level of theory was unable to simulate the initial formal electrophilic substitution reaction proposed as the arenium ion C could not be minimized. Therefore based on current results the preferred pathway is as follows: (1) nucleophilic substitution of the acyl chloride to form five-coordinate acylplatinum complex with a barrier of 21.7083 k cal/mol (B), followed by (2) 1,2-migration of the acyl group from the platinum to the metalated carbon to form a Pt-arene n-complex or platinacyclopropane with a barrier of 15.0713 kcal/mol (E). Lastly, (3) Re-aromatization of E leads to the acylated product P with a barrier of 35.3138 kcal/mol. Further probing and key mechanistic results will be presented.
General note	Presented to the faculty of the Department of Chemistry
General note	Advisor: Yumin Li
General note	Title from PDF t.p. (viewed March 23, 2020).
Dissertation note	M.S. East Carolina University 2019.
Bibliography note	Includes bibliographical references.
Technical details	System requirements: Adobe Reader.
Technical details	Mode of access: World Wide Web.

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