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Oxygen atom transfer to half-sandwic...

Turlington, Christopher R.

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Oxygen atom transfer to half-sandwich complexes of iridium and rhodium.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Oxygen atom transfer to half-sandwich complexes of iridium and rhodium./
Author:	Turlington, Christopher R.
Description:	225 p.
Notes:	Source: Dissertation Abstracts International, Volume: 76-09(E), Section: B.
Contained By:	Dissertation Abstracts International76-09B(E).
Subject:	Analytical chemistry. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3703968
ISBN:	9781321761030

Oxygen atom transfer to half-sandwich complexes of iridium and rhodium.
Turlington, Christopher R.

Oxygen atom transfer to half-sandwich complexes of iridium and rhodium. - 225 p.

Source: Dissertation Abstracts International, Volume: 76-09(E), Section: B.

Thesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2015.

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

The oxidation chemistry of half-sandwich iridium and rhodium complexes was explored. Iridium(Cp*) and rhodium(Cp*) complexes were prepared with various bidentate ligands and then reacted with oxygen atom transfer reagents. While oxidative degradation of the organic ligands was observed when using the oxygen atom transfer reagents iodosylbenzene and dimethyldioxirane, clean products were obtained when using a soluble derivative of iodosylbenzene, 2- tert-butylsulfonyliodosylbenzene (sPhIO). Oxidation reactions with sPhIO were typically conducted at low temperatures to increase the chance of observing reactive intermediates. It was found that the bidentate ligand 2-phenylpyridine was susceptible to insertion reactions at both metal centers. Oxygen atom insertion was observed into the rhodium-carbon bond of coordinated 2-phenylpyridine in a rhodium(Cp*) complex. Oxygen atom insertion was not observed in the analogous iridium complex; instead, an isoelectronic nitrene insertion into the iridium-carbon bond of 2-phenylpyridine occurred upon oxygen atom transfer to a coordinated nitrile ligand of the iridium(Cp*) complex. Subsequent oxygen atom transfer to the nitrene insertion compound occurred, but the iridium product could not be identified. The possible intermediacy of high-valent iridium and rhodium complexes is discussed. In addition, model iridium complexes were prepared with oxidized phenylpyridine ligands. Their reactivity suggested deactivation pathways involving the bidentate ligands of common water oxidation catalysts.

ISBN: 9781321761030Subjects--Topical Terms:

3168300
Analytical chemistry.

Oxygen atom transfer to half-sandwich complexes of iridium and rhodium.
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100 1 $a Turlington, Christopher R. $3 3181335
245 1 0 $a Oxygen atom transfer to half-sandwich complexes of iridium and rhodium.
300 $a 225 p.
500 $a Source: Dissertation Abstracts International, Volume: 76-09(E), Section: B.
500 $a Advisers: Joseph L. Templeton; Maurice Brookhart.
502 $a Thesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2015.
506 $a This item must not be sold to any third party vendors.
506 $a This item must not be added to any third party search indexes.
520 $a The oxidation chemistry of half-sandwich iridium and rhodium complexes was explored. Iridium(Cp*) and rhodium(Cp*) complexes were prepared with various bidentate ligands and then reacted with oxygen atom transfer reagents. While oxidative degradation of the organic ligands was observed when using the oxygen atom transfer reagents iodosylbenzene and dimethyldioxirane, clean products were obtained when using a soluble derivative of iodosylbenzene, 2- tert-butylsulfonyliodosylbenzene (sPhIO). Oxidation reactions with sPhIO were typically conducted at low temperatures to increase the chance of observing reactive intermediates. It was found that the bidentate ligand 2-phenylpyridine was susceptible to insertion reactions at both metal centers. Oxygen atom insertion was observed into the rhodium-carbon bond of coordinated 2-phenylpyridine in a rhodium(Cp*) complex. Oxygen atom insertion was not observed in the analogous iridium complex; instead, an isoelectronic nitrene insertion into the iridium-carbon bond of 2-phenylpyridine occurred upon oxygen atom transfer to a coordinated nitrile ligand of the iridium(Cp*) complex. Subsequent oxygen atom transfer to the nitrene insertion compound occurred, but the iridium product could not be identified. The possible intermediacy of high-valent iridium and rhodium complexes is discussed. In addition, model iridium complexes were prepared with oxidized phenylpyridine ligands. Their reactivity suggested deactivation pathways involving the bidentate ligands of common water oxidation catalysts.
590 $a School code: 0153.
650 4 $a Analytical chemistry. $3 3168300
650 4 $a Organic chemistry. $3 523952
650 4 $a Inorganic chemistry. $3 3173556
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710 2 $a The University of North Carolina at Chapel Hill. $b Chemistry. $3 1021872
773 0 $t Dissertation Abstracts International $g 76-09B(E).
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791 $a Ph.D.
792 $a 2015
793 $a English
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