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Synthesis and spectroscopic characte...

Ramdhanie, Bobby.

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Synthesis and spectroscopic characterization of metallo-triazacorroles.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Synthesis and spectroscopic characterization of metallo-triazacorroles./
作者:	Ramdhanie, Bobby.
面頁冊數:	299 p.
附註:	Source: Dissertation Abstracts International, Volume: 64-10, Section: B, page: 4934.
Contained By:	Dissertation Abstracts International64-10B.
標題:	Chemistry, Inorganic. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3107565
ISBN:	0496551140

Synthesis and spectroscopic characterization of metallo-triazacorroles.
Ramdhanie, Bobby.

Synthesis and spectroscopic characterization of metallo-triazacorroles. - 299 p.

Source: Dissertation Abstracts International, Volume: 64-10, Section: B, page: 4934.

Thesis (Ph.D.)--The Johns Hopkins University, 2004.

In recent years, there has been renewed interest in the synthesis and reactivity of corroles. Corroles are ring contracted analogs of porphyrins in which one meso-carbon atom has been removed. Much of the interest in corroles comes from their ability to stabilize high-valent metal oxidation states. We believe that by studying these metallocorroles, we may gain a better understanding of the role high oxidation state complexes in a number of important industrial and biological applications.

ISBN: 0496551140Subjects--Topical Terms:

517253
Chemistry, Inorganic.

Synthesis and spectroscopic characterization of metallo-triazacorroles.
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245 1 0 $a Synthesis and spectroscopic characterization of metallo-triazacorroles.
300 $a 299 p.
500 $a Source: Dissertation Abstracts International, Volume: 64-10, Section: B, page: 4934.
500 $a Adviser: David P. Goldberg.
502 $a Thesis (Ph.D.)--The Johns Hopkins University, 2004.
520 $a In recent years, there has been renewed interest in the synthesis and reactivity of corroles. Corroles are ring contracted analogs of porphyrins in which one meso-carbon atom has been removed. Much of the interest in corroles comes from their ability to stabilize high-valent metal oxidation states. We believe that by studying these metallocorroles, we may gain a better understanding of the role high oxidation state complexes in a number of important industrial and biological applications.
520 $a Chapter 1 describes the synthesis and spectroscopic characterization of a new type of corrole compound in which the meso-carbon atom has been replaced with nitrogen atoms. This new type of corrole system, called triazacorrole or corrolazine (Cz) can be prepared by a six step synthesis on a multi-gram scale in good yield. The synthesis involves a tetraazaporphyrin (TBP) 8PzH2, as the starting material. When the tetraazaporphyrin, or porphyrazine is reacted with PBr3; the ring-contracted triazacorrole [(TBP)8CzP(OH)]OH is obtained with a phosphorus atom bound to the internal cavity. The phosphorus atom is removed through a reductive demetallation reaction affording the metal-free triazacorrole (TBP)8CzH 3. The metal-free triazacorrole is the key precursor to the other metallocorroles in the succeeding chapters.
520 $a In Chapter 2, the synthesis and spectroscopic characterization of three cobalt triazacorroles (TBP)8CzCo, (TBP)8CzCoPPh 3, and (TBP)8CzCo(pyr)2. (TBP)8CzCoPPh 3, A study involving the titration of pyridine to the cobalt complex (TBP)8CzCo, was carried out to measure the binding constant of the two pyridine ligands. This study shows that because the corrolazine cavity is smaller than normal corroles and because of the electronegativity of the three meso-nitrogen atoms, the cobalt ion is more Lewis acidic when bound to the internal cavity of a triazacorrole than in normal corrole ligands.
520 $a Chapter 3 expands upon cobalt triazacorrole chemistry in Chapter 2. In order to study formally high-valent cobalt (IV) triazacorroles, two new cobalt triazacorroles (TBP)8CzCoCN and (TBP)8CzCoCCSiPPh 3 have been prepared. Both of these compounds have been synthesized and characterized by normal spectroscopic techniques (1H NMR, IR, UV-vis) as well as EPR and magnetic susceptibility measurements. (TBP) 8CzCoCCSiPPh3 has also been characterized by X-ray crystallography. This chapter also explores how dioxygen also plays a major role in the formation of our cobalt triazacorroles and its ability to bind to the reduced cobalt (II) triazacorrole anion. This is the first reference of dioxygen binding to a cobalt corrole.
520 $a In Chapter 4, a number of other transition metal triazacorroles including [(TBP)8CzVIVO]-, (TBP) 8Cz+.NiII and (TBP) 8CzCuIII that have been synthesized and spectroscopically characterized by 1H NMR, UV-Vis, IR, and EPR spectroscopy. (Abstract shortened by UMI.)
590 $a School code: 0098.
650 4 $a Chemistry, Inorganic. $3 517253
650 4 $a Chemistry, Physical. $3 560527
650 4 $a Chemistry, Analytical. $3 586156
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690 $a 0494
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710 2 0 $a The Johns Hopkins University. $3 1017431
773 0 $t Dissertation Abstracts International $g 64-10B.
790 1 0 $a Goldberg, David P., $e advisor
790 $a 0098
791 $a Ph.D.
792 $a 2004
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3107565