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Binuclear non-heme iron complexes and their reactive intermediates :Kinetics and energetics of formation.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Binuclear non-heme iron complexes and their reactive intermediates :
其他題名:	Kinetics and energetics of formation.
作者:	Spuches, Anne Marie.
面頁冊數:	438 p.
附註:	Director: John Philip Caradonna.
附註:	Source: Dissertation Abstracts International, Volume: 64-10, Section: B, page: 4936.
Contained By:	Dissertation Abstracts International64-10B.
標題:	Chemistry, Inorganic.
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3109466
ISBN:	0496570080

Binuclear non-heme iron complexes and their reactive intermediates :Kinetics and energetics of formation.
Spuches, Anne Marie.

Binuclear non-heme iron complexes and their reactive intermediates :Kinetics and energetics of formation. [electronic resource] - 438 p.

Director: John Philip Caradonna.

Thesis (Ph.D.)--Yale University, 2003.

It was previously shown that the anaerobic reaction of [Fe2 2+(H2Hbamb)2(N-MeIm)2 ], (H2Hbamb = 2,3-bis(2-hydroxybenzamido)2,3-dimethylbutane, N-MeIm = N-methylimidazole), with various oxygen atom donors at low temperatures resulted in the formation of a new intermediate species capable of the hydroxylation of alkanes (alcohol:ketone > 55:1), epoxidation of alkenes, and oxidation of sulfides. In addition, a similar intermediate species was observed upon the addition of an oxygen atom donor to the mixed valence analog. More recently, complexes containing variations in the ligand backbone were synthesized and spectroscopically characterized. Low temperature UV-Vis studies utilizing the diferrous complexes and para-cyano-dimethylaniline N-oxide (p-CN-DMANO) as an oxygen atom donor revealed the growth of a chromophore similar to that of the intermediate species previously observed. Furthermore, these intermediates displayed similar behavior and decayed to the respective diamagnetic mu-oxo complexes upon warming as observed by UV-Vis and EPR spectroscopies. In order to develop an understanding of the energetics of formation and decay of the intermediates generated, kinetic studies were conducted at various temperatures, and thermodynamic parameters obtained. The results correlate with ligand rigidity. Kinetics and activation parameters were also obtained for the reaction between p-CN-DMANO and the mixed valence species thus obtaining insight into the effect of ligand reorganization upon intermediate formation.

ISBN: 0496570080Subjects--Topical Terms:

197298
Chemistry, Inorganic.

Binuclear non-heme iron complexes and their reactive intermediates :Kinetics and energetics of formation.
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520 # $a It was previously shown that the anaerobic reaction of [Fe2 2+(H2Hbamb)2(N-MeIm)2 ], (H2Hbamb = 2,3-bis(2-hydroxybenzamido)2,3-dimethylbutane, N-MeIm = N-methylimidazole), with various oxygen atom donors at low temperatures resulted in the formation of a new intermediate species capable of the hydroxylation of alkanes (alcohol:ketone > 55:1), epoxidation of alkenes, and oxidation of sulfides. In addition, a similar intermediate species was observed upon the addition of an oxygen atom donor to the mixed valence analog. More recently, complexes containing variations in the ligand backbone were synthesized and spectroscopically characterized. Low temperature UV-Vis studies utilizing the diferrous complexes and para-cyano-dimethylaniline N-oxide (p-CN-DMANO) as an oxygen atom donor revealed the growth of a chromophore similar to that of the intermediate species previously observed. Furthermore, these intermediates displayed similar behavior and decayed to the respective diamagnetic mu-oxo complexes upon warming as observed by UV-Vis and EPR spectroscopies. In order to develop an understanding of the energetics of formation and decay of the intermediates generated, kinetic studies were conducted at various temperatures, and thermodynamic parameters obtained. The results correlate with ligand rigidity. Kinetics and activation parameters were also obtained for the reaction between p-CN-DMANO and the mixed valence species thus obtaining insight into the effect of ligand reorganization upon intermediate formation.
520 # $a The [Fe22+(H2Hbamb)2( N-MeIm)2] complex was recently shown capable of the heterolytic cleavage of the O-O bond of the alky hydroperoxide, 2-methyl-1-phenyl-2-propyl (MPPH). Furthermore, the diferrous complex was capable of the same catalytic oxidations in the presence of MPPH. The stoichiometric addition of MPPH to [Fe22+(H2Hbamb)2( N-MeIm)2] at low temperatures revealed the generation of the same intermediate species observed in previous studies. The rate of formation was also determined for this process and was compared to the formation of the intermediate generated from phenylperacetic acid (PPAA) and p-CN-DMANO at -45°C in two different solvent systems. The results indicate a dependence on solvent and oxygen atom source on intermediate formation kinetics.
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