Mechanistic Study on Photogeneration of Nitrogen Based Reactive Intermediates via Transient Spectroscopy & Infrared Matrix Isolation Study on Organometallic Reactions with Ozone Forming Metal Oxides
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| Language: | English |
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University of Cincinnati / OhioLINK
2017
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| Online Access: | http://rave.ohiolink.edu/etdc/view?acc_num=ucin1504802160622286 |
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ndltd-OhioLink-oai-etd.ohiolink.edu-ucin1504802160622286 |
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oai_dc |
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NDLTD |
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English |
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Organic Chemistry Nitrenes Laser flash photolysis matrix isolation metal oxide EPR azides |
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Organic Chemistry Nitrenes Laser flash photolysis matrix isolation metal oxide EPR azides Sriyarathne, H. Dushanee M. Mechanistic Study on Photogeneration of Nitrogen Based Reactive Intermediates via Transient Spectroscopy & Infrared Matrix Isolation Study on Organometallic Reactions with Ozone Forming Metal Oxides |
| author |
Sriyarathne, H. Dushanee M. |
| author_facet |
Sriyarathne, H. Dushanee M. |
| author_sort |
Sriyarathne, H. Dushanee M. |
| title |
Mechanistic Study on Photogeneration of Nitrogen Based Reactive Intermediates via Transient Spectroscopy & Infrared Matrix Isolation Study on Organometallic Reactions with Ozone Forming Metal Oxides |
| title_short |
Mechanistic Study on Photogeneration of Nitrogen Based Reactive Intermediates via Transient Spectroscopy & Infrared Matrix Isolation Study on Organometallic Reactions with Ozone Forming Metal Oxides |
| title_full |
Mechanistic Study on Photogeneration of Nitrogen Based Reactive Intermediates via Transient Spectroscopy & Infrared Matrix Isolation Study on Organometallic Reactions with Ozone Forming Metal Oxides |
| title_fullStr |
Mechanistic Study on Photogeneration of Nitrogen Based Reactive Intermediates via Transient Spectroscopy & Infrared Matrix Isolation Study on Organometallic Reactions with Ozone Forming Metal Oxides |
| title_full_unstemmed |
Mechanistic Study on Photogeneration of Nitrogen Based Reactive Intermediates via Transient Spectroscopy & Infrared Matrix Isolation Study on Organometallic Reactions with Ozone Forming Metal Oxides |
| title_sort |
mechanistic study on photogeneration of nitrogen based reactive intermediates via transient spectroscopy & infrared matrix isolation study on organometallic reactions with ozone forming metal oxides |
| publisher |
University of Cincinnati / OhioLINK |
| publishDate |
2017 |
| url |
http://rave.ohiolink.edu/etdc/view?acc_num=ucin1504802160622286 |
| work_keys_str_mv |
AT sriyarathnehdushaneem mechanisticstudyonphotogenerationofnitrogenbasedreactiveintermediatesviatransientspectroscopyinfraredmatrixisolationstudyonorganometallicreactionswithozoneformingmetaloxides |
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1719452927141085184 |
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ndltd-OhioLink-oai-etd.ohiolink.edu-ucin15048021606222862021-08-03T07:04:08Z Mechanistic Study on Photogeneration of Nitrogen Based Reactive Intermediates via Transient Spectroscopy & Infrared Matrix Isolation Study on Organometallic Reactions with Ozone Forming Metal Oxides Sriyarathne, H. Dushanee M. Organic Chemistry Nitrenes Laser flash photolysis matrix isolation metal oxide EPR azides The work outline in this dissertation, we report the possible mechanisms for the photogeneration of carbon and nitrogen reactive intermediates by studying their excited state reactivity at room temperature and cryogenic temperatures (4 K – 77 K) in both solution and solid state.The feasibility of high energy photochemical pathways and the verifications of intermediates to validate the reaction mechanisms are estimated using DFT, Gaussian 09 computational platform. In Chapter 02, we look at the α-phenyl substituted isoxazole in cryogenic matrices with the focus of capturing azirines from vinylnitrenes. We demonstrated that conjugation of the α-phenyl group to the vinylnitrene moiety renders it more flexible and lower the rotational barrier than vinylnitrenes with a-methyl substituents, and therefore facilitate intersystem crossing of vinylnitrene to azirine, rather than ketenimine. In Chapter 03, we rationalizes and provides physical insight into vinylnitrene stability at room temperature and low temperature. We theorize that the unique reactivity of triplet vinylnitrene is due to their flexibility which is a reflection of their 1,3-biradical character. Moreover, triplet vinylnitrenes can be stabilized by limiting the flexibility of the built in sensitizer and the vinyl C=C bond at room temperature and low temperature.In Chapter 04, we explore the thermal and photochemical reactions of (CH3)3Ga and O3 to form metal oxides, using a combination of matrix isolation, infrared spectroscopy and theoretical calculations. The potential mechanisms for the formation of intermediates were discussed.In Chapter 05, we report the photochemistry of β γ-vinylarylketone with a built-in triplet sensitizer. This work demonstrated that intramolecular sensitization of a simple alkenes can be used to form triplet 1,2-biradicals with the two radical centers localized on the adjacent carbon atoms, which can potentially be used for cis-trans isomerization of simple alkenes in applications.In Chapter 06, we investigated the thermal and photochemical reactions of (CH3)3Al and O3 using a combination of matrix isolation, infrared spectroscopy and theoretical calculations. The potential mechanisms for the formation of intermediates were discussed in this chapter which has an important impact on semiconducting metal oxide thin film formation.In Chapter 07, we conducted a theoretical study on the carbon centered radical reaction with molecular oxygen to investigate the factors determining the radical reactivity with oxygen. Herein we demonstrate that the calculated transition state barrier energy can be used to predict which radical will not react with oxygen and which will react. Further, the difference in transition state barrier energy can be explained by focusing on the charge distribution in the transition structure. In Chapter 08, we were interested in studying the photoreactivity of azidovinylketones using a built in triplet sensitizer and characterize the intermediates formed upon excitation at cryogenic temperature. In Chapter 09, we report the photoreactivity of a-diazido acetophenone derivatives containing an intramolecular triplet sensitizer. We demonstrated that germinal diazido alkane undergo alpha-cleavage at room temperature and at cryogenic temperature it undergo different reactivity resulting the formation of alkylnitrenes. 2017-10-30 English text University of Cincinnati / OhioLINK http://rave.ohiolink.edu/etdc/view?acc_num=ucin1504802160622286 http://rave.ohiolink.edu/etdc/view?acc_num=ucin1504802160622286 unrestricted This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws. |