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Catalysis of hydrocarbon oxidation b...

Shalyaev, Kirill V.

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Catalysis of hydrocarbon oxidation by polyhalogenated ruthenium porphyrins and studies on the origins of enantioselectivity in metalloporphyrin catalyzed olefin epoxidations.

Record Type:	Language materials, printed : Monograph/item
Title/Author:	Catalysis of hydrocarbon oxidation by polyhalogenated ruthenium porphyrins and studies on the origins of enantioselectivity in metalloporphyrin catalyzed olefin epoxidations./
Author:	Shalyaev, Kirill V.
Description:	201 p.
Notes:	Source: Dissertation Abstracts International, Volume: 60-02, Section: B, page: 0643.
Contained By:	Dissertation Abstracts International60-02B.
Subject:	Chemistry, Inorganic. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9920463
ISBN:	9780599196162

Catalysis of hydrocarbon oxidation by polyhalogenated ruthenium porphyrins and studies on the origins of enantioselectivity in metalloporphyrin catalyzed olefin epoxidations.
Shalyaev, Kirill V.

Catalysis of hydrocarbon oxidation by polyhalogenated ruthenium porphyrins and studies on the origins of enantioselectivity in metalloporphyrin catalyzed olefin epoxidations. - 201 p.

Source: Dissertation Abstracts International, Volume: 60-02, Section: B, page: 0643.

Thesis (Ph.D.)--Princeton University, 1998.

Polyhalogenated ruthenium porphyrin complexes such as RuII(TPFPP)(CO) were found to be efficient catalysts for the oxygenation of hydrocarbons including secondary alkanes and benzene in the presence of 2,6-dichloropyridine N-oxide as oxidant under mild non-acidic conditions. Up to 15,000 turnovers and rates of 800 TO/min were obtained in hydroxylation of adamantane. The hydroxylation of cis-decalin gave cis-9-decalol and cis-decalin-9,10-diol, exclusively. Benzene was oxidized to benzoquinone.

ISBN: 9780599196162Subjects--Topical Terms:

517253
Chemistry, Inorganic.

Catalysis of hydrocarbon oxidation by polyhalogenated ruthenium porphyrins and studies on the origins of enantioselectivity in metalloporphyrin catalyzed olefin epoxidations.
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100 1 $a Shalyaev, Kirill V. $3 1297798
245 1 0 $a Catalysis of hydrocarbon oxidation by polyhalogenated ruthenium porphyrins and studies on the origins of enantioselectivity in metalloporphyrin catalyzed olefin epoxidations.
300 $a 201 p.
500 $a Source: Dissertation Abstracts International, Volume: 60-02, Section: B, page: 0643.
502 $a Thesis (Ph.D.)--Princeton University, 1998.
520 $a Polyhalogenated ruthenium porphyrin complexes such as RuII(TPFPP)(CO) were found to be efficient catalysts for the oxygenation of hydrocarbons including secondary alkanes and benzene in the presence of 2,6-dichloropyridine N-oxide as oxidant under mild non-acidic conditions. Up to 15,000 turnovers and rates of 800 TO/min were obtained in hydroxylation of adamantane. The hydroxylation of cis-decalin gave cis-9-decalol and cis-decalin-9,10-diol, exclusively. Benzene was oxidized to benzoquinone.
520 $a Based on the kinetic and spectroscopic evidence RuVI(TPFPP)(O) 2, RuIV(TPFPP)(O), RuII(TPFPP)(CO) and RuIV(TPFPP)Cl2 observed during catalysis have been ruled out as candidates for the active intermediates responsible for the high efficiencies and turnover rates. A mechanism is proposed which incorporates a "slow" oxidation cycle, mediated by oxoRu(IV) and trans-dioxoRu(VI) porphyrin complexes, and a "fast" cycle where metastable Ru(III) and oxoRu(V) intermediates play an important role. The fastest rates of adamantane hydroxylation and cyclohexene epoxidation were achieved with RuIV(TPFPP)Cl2 catalyst in the presence of zinc amalgam. This reductive activation is consistent with the formation of an active Ru(III) intermediate in situ by a one-electron reduction of the Ru(IV) porphyrin. The synthesis and EPR characterization of authentic Ru(III) alkoxy porphyrin complexes is described.
520 $a Polyhalogenated ruthenium porphyrin complexes, RuII(TPFPP)(CO) and RuII(TPFPPBr8)(CO), were covalently bound to 3-aminopropylsilica. The new heterogeneous catalysts were found to be efficient, robust and selective in oxygenation of a variety of hydrocarbons with 2,6-dichloropyridine N-oxide. Over 6,000 catalytic turnovers was obtained in hydroxylation of cyclohexane. Epoxidation of cis-stilbene stereospecifically afforded cis-epoxide in up to 84% yield. Cis-decalin was oxidized to cis-9-decalinol in 90% yield. No significant leaching of ruthenium porphyrin from the solid support was found under the conditions of oxidative catalysis.
520 $a The origins of chiral induction by asymmetric porphyrin and salen complexes were investigated by FT-NMR T1 relaxation techniques. The transition state for olefin epoxidation with high-valent metal-oxo species was modeled by coordinating epoxides to paramagnetic copper complexes of the corresponding ligands. The epoxide enantiomer that better fit the chiral cavity of the catalyst, as revealed by T1 relaxation measurements, was also the major product of catalytic olefin epoxidation. These results are consistent with the 'lock-and-key' mechanism of asymmetric catalysis by metalloporphyrins.
590 $a School code: 0181.
650 4 $a Chemistry, Inorganic. $3 517253
650 4 $a Chemistry, Organic. $3 516206
690 $a 0488
690 $a 0490
710 2 0 $a Princeton University. $3 645579
773 0 $t Dissertation Abstracts International $g 60-02B.
790 $a 0181
791 $a Ph.D.
792 $a 1998
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9920463