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Polarization effects on the electron...

Rau, Nathan James.

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Polarization effects on the electronic structures of organic reactive intermediates.

紀錄類型:	書目-語言資料,印刷品 : Monograph/item
正題名/作者:	Polarization effects on the electronic structures of organic reactive intermediates./
作者:	Rau, Nathan James.
面頁冊數:	225 p.
附註:	Source: Dissertation Abstracts International, Volume: 74-12(E), Section: B.
Contained By:	Dissertation Abstracts International74-12B(E).
標題:	Chemistry, General. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3592090
ISBN:	9781303329524

Polarization effects on the electronic structures of organic reactive intermediates.
Rau, Nathan James.

Polarization effects on the electronic structures of organic reactive intermediates. - 225 p.

Source: Dissertation Abstracts International, Volume: 74-12(E), Section: B.

Thesis (Ph.D.)--Purdue University, 2013.

This dissertation focuses on the study of gas-phase organic reactive (often radical) intermediates using flowing-afterglow mass spectrometry, and mainly includes the study of pyridynes (diradicals having the formula C 5H3N) and aromatic nitrenes. The gas-phase enthalpy of formation of 2,3-, 2,4-, and 3,4-pyridyne were determined using a thermochemical cycle and by measuring the proton affinity and chloride bond dissociation energy of deprotonated 2- and 3-chloropyridine. These results agree well with theoretical calculations and are compared to benzynes and their aromatic precursors (pyridine and benzene). It was found that polarizing effects stabilize 2,4-pyridyne compared to m-benzyne and destabilize 2,3-pyridyne compared to o-benzyne.

ISBN: 9781303329524Subjects--Topical Terms:

1021807
Chemistry, General.

Polarization effects on the electronic structures of organic reactive intermediates.
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245 1 0 $a Polarization effects on the electronic structures of organic reactive intermediates.
300 $a 225 p.
500 $a Source: Dissertation Abstracts International, Volume: 74-12(E), Section: B.
500 $a Adviser: Paul Wenthold.
502 $a Thesis (Ph.D.)--Purdue University, 2013.
520 $a This dissertation focuses on the study of gas-phase organic reactive (often radical) intermediates using flowing-afterglow mass spectrometry, and mainly includes the study of pyridynes (diradicals having the formula C 5H3N) and aromatic nitrenes. The gas-phase enthalpy of formation of 2,3-, 2,4-, and 3,4-pyridyne were determined using a thermochemical cycle and by measuring the proton affinity and chloride bond dissociation energy of deprotonated 2- and 3-chloropyridine. These results agree well with theoretical calculations and are compared to benzynes and their aromatic precursors (pyridine and benzene). It was found that polarizing effects stabilize 2,4-pyridyne compared to m-benzyne and destabilize 2,3-pyridyne compared to o-benzyne.
520 $a Using ion-molecule reactions and measured rate constants, the electronic structure of a series of phenylnitrenes (triplet diradical, Ph-N) with anionic substituents as well as deprotonated benzaldehyde imines (singlet, PhCHN) with neutral substituents were characterized. Introducing strong anionic pi-donors (CH2- and O-) to phenylnitrene stabilizes the closed-shell singlet by more than 30 kcal/mol, such that it becomes the ground electronic state (or degenerate with the triplet) which then resembles a deprotonated imine. Conversely, addition of a strong pi-withdrawing group (-NO2) to deprotonated benzaldehyde imine induces the opposite effect, stabilizing the triplet, nitrene-like state, to the point where it is the ground state. These complementary approaches show that the nitrene/imine character is based upon the spin-state of the ion and can be "tuned" by using appropriate substitution of strong pi-donating/withdrawing groups. Also included is preliminary research on the hydride donation chemistry of benzaldimides and the formation of dithioformic acid in the reaction of benzaldimides and CS2.
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