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Applications of a Pendant Amine for ...

Christman, William E. .

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Applications of a Pendant Amine for C-H and C-Cl Activation at PdII.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Applications of a Pendant Amine for C-H and C-Cl Activation at PdII./
Author:	Christman, William E. .
Published:	Ann Arbor : ProQuest Dissertations & Theses, : 2020,
Description:	200 p.
Notes:	Source: Dissertations Abstracts International, Volume: 82-05, Section: B.
Contained By:	Dissertations Abstracts International82-05B.
Subject:	Chemistry. -
Online resource:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=28089799
ISBN:	9798691213571

Applications of a Pendant Amine for C-H and C-Cl Activation at PdII.
Christman, William E. .

Applications of a Pendant Amine for C-H and C-Cl Activation at PdII. - Ann Arbor : ProQuest Dissertations & Theses, 2020 - 200 p.

Source: Dissertations Abstracts International, Volume: 82-05, Section: B.

Thesis (Ph.D.)--University of Wyoming, 2020.

This item must not be sold to any third party vendors.

Secondary coordination sphere interactions can assist in the stabilization of high energy intermediates and accelerate rate-limiting steps in homogeneous transition metal chemistry. The interplay between the primary and secondary coordination spheres is controlled by both the functional group of the pendant moiety and the electronic properties of the transition metal. The following research, through a combination of experimental and computational methods, identifies the roles of a pendant amine that has been integrated into PdII complexes. When paired with an electrophilic PdII species, the pendant amine serves as a thermodynamic base for heterolytic C-H activation. Accurate estimations of PdII(η2-arene) C-H acidity could be achieved by determining the absolute pKa of the protonated pendant amine and relating that to calculated equilibria of relevant reactive intermediates. The same pendant amine can also kinetically assist C-Cl activation when incorporated into a nucleophilic PdII compound and demonstrated how a nucleophile in the secondary coordination sphere can modulate the oxidizing potential of a transition metal complex. An in-depth perspective on the chemistry of PdII complexes bearing a pendant amine in the secondary-coordination sphere is hereby presented.

ISBN: 9798691213571Subjects--Topical Terms:

516420
Chemistry.
Subjects--Index Terms:

C-H acidity

Applications of a Pendant Amine for C-H and C-Cl Activation at PdII.
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100 1 $a Christman, William E. . $3 3564260
245 1 0 $a Applications of a Pendant Amine for C-H and C-Cl Activation at PdII.
260 1 $a Ann Arbor : $b ProQuest Dissertations & Theses, $c 2020
300 $a 200 p.
500 $a Source: Dissertations Abstracts International, Volume: 82-05, Section: B.
500 $a Advisor: Hulley, Elliott B.
502 $a Thesis (Ph.D.)--University of Wyoming, 2020.
506 $a This item must not be sold to any third party vendors.
520 $a Secondary coordination sphere interactions can assist in the stabilization of high energy intermediates and accelerate rate-limiting steps in homogeneous transition metal chemistry. The interplay between the primary and secondary coordination spheres is controlled by both the functional group of the pendant moiety and the electronic properties of the transition metal. The following research, through a combination of experimental and computational methods, identifies the roles of a pendant amine that has been integrated into PdII complexes. When paired with an electrophilic PdII species, the pendant amine serves as a thermodynamic base for heterolytic C-H activation. Accurate estimations of PdII(η2-arene) C-H acidity could be achieved by determining the absolute pKa of the protonated pendant amine and relating that to calculated equilibria of relevant reactive intermediates. The same pendant amine can also kinetically assist C-Cl activation when incorporated into a nucleophilic PdII compound and demonstrated how a nucleophile in the secondary coordination sphere can modulate the oxidizing potential of a transition metal complex. An in-depth perspective on the chemistry of PdII complexes bearing a pendant amine in the secondary-coordination sphere is hereby presented.
590 $a School code: 0264.
650 4 $a Chemistry. $3 516420
650 4 $a Inorganic chemistry. $3 3173556
650 4 $a Physical chemistry. $3 1981412
653 $a C-H acidity
653 $a Electrophilic C-H activation
653 $a Oxidative addition
653 $a Pd(II)
653 $a Pendant base
653 $a Pendant nucleophile
690 $a 0485
690 $a 0488
690 $a 0494
710 2 $a University of Wyoming. $b Chemistry. $3 1680463
773 0 $t Dissertations Abstracts International $g 82-05B.
790 $a 0264
791 $a Ph.D.
792 $a 2020
793 $a English
856 4 0 $u https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=28089799