Anthracene-induced turnover enhancement in the manganese porphyrin-catalyzed epoxidation of olefins

Melissa L. Merlau, So Hye Cho, Shih Sheng Sun, SonBinh T. Nguyen, Joseph T Hupp

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

Anthracene and related compounds function as lifetime-extending cofactors in the (mesotetraphenylporphine)MnIII chloride-catalyzed epoxidation of olefins. An experiment with a chiral porphyrin catalyst shows that enantioselectivity is preserved in the presence of the cofactor. Additional experiments show that (a) turnover number enhancement is greatest for the least reactive substrates, (b) derivatization of anthracene at the 9 and 10 positions largely eliminates the enhancement effect, and (c) anthracene is ultimately converted to anthraquinone. The origin of the observed enhancements is in the reaction of anthracene with the normally unreactive dimeric oxo-bridged form of the catalyst. This reaction, which produces anthraquinone, regenerates the catalytically active monomeric form of the manganese porphyrin.

Original languageEnglish
Pages (from-to)5523-5529
Number of pages7
JournalInorganic Chemistry
Volume44
Issue number15
DOIs
Publication statusPublished - Jul 25 2005

Fingerprint

epoxidation
Epoxidation
Porphyrins
Alkenes
Manganese
anthracene
porphyrins
alkenes
manganese
Anthraquinones
anthraquinones
augmentation
catalysts
Catalysts
Enantioselectivity
Chlorides
Experiments
chlorides
life (durability)
Substrates

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Anthracene-induced turnover enhancement in the manganese porphyrin-catalyzed epoxidation of olefins. / Merlau, Melissa L.; Cho, So Hye; Sun, Shih Sheng; Nguyen, SonBinh T.; Hupp, Joseph T.

In: Inorganic Chemistry, Vol. 44, No. 15, 25.07.2005, p. 5523-5529.

Research output: Contribution to journalArticle

Merlau, Melissa L. ; Cho, So Hye ; Sun, Shih Sheng ; Nguyen, SonBinh T. ; Hupp, Joseph T. / Anthracene-induced turnover enhancement in the manganese porphyrin-catalyzed epoxidation of olefins. In: Inorganic Chemistry. 2005 ; Vol. 44, No. 15. pp. 5523-5529.
@article{cdd2192af82749178cdf6232ce7a56a1,
title = "Anthracene-induced turnover enhancement in the manganese porphyrin-catalyzed epoxidation of olefins",
abstract = "Anthracene and related compounds function as lifetime-extending cofactors in the (mesotetraphenylporphine)MnIII chloride-catalyzed epoxidation of olefins. An experiment with a chiral porphyrin catalyst shows that enantioselectivity is preserved in the presence of the cofactor. Additional experiments show that (a) turnover number enhancement is greatest for the least reactive substrates, (b) derivatization of anthracene at the 9 and 10 positions largely eliminates the enhancement effect, and (c) anthracene is ultimately converted to anthraquinone. The origin of the observed enhancements is in the reaction of anthracene with the normally unreactive dimeric oxo-bridged form of the catalyst. This reaction, which produces anthraquinone, regenerates the catalytically active monomeric form of the manganese porphyrin.",
author = "Merlau, {Melissa L.} and Cho, {So Hye} and Sun, {Shih Sheng} and Nguyen, {SonBinh T.} and Hupp, {Joseph T}",
year = "2005",
month = "7",
day = "25",
doi = "10.1021/ic0505596",
language = "English",
volume = "44",
pages = "5523--5529",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "15",

}

TY - JOUR

T1 - Anthracene-induced turnover enhancement in the manganese porphyrin-catalyzed epoxidation of olefins

AU - Merlau, Melissa L.

AU - Cho, So Hye

AU - Sun, Shih Sheng

AU - Nguyen, SonBinh T.

AU - Hupp, Joseph T

PY - 2005/7/25

Y1 - 2005/7/25

N2 - Anthracene and related compounds function as lifetime-extending cofactors in the (mesotetraphenylporphine)MnIII chloride-catalyzed epoxidation of olefins. An experiment with a chiral porphyrin catalyst shows that enantioselectivity is preserved in the presence of the cofactor. Additional experiments show that (a) turnover number enhancement is greatest for the least reactive substrates, (b) derivatization of anthracene at the 9 and 10 positions largely eliminates the enhancement effect, and (c) anthracene is ultimately converted to anthraquinone. The origin of the observed enhancements is in the reaction of anthracene with the normally unreactive dimeric oxo-bridged form of the catalyst. This reaction, which produces anthraquinone, regenerates the catalytically active monomeric form of the manganese porphyrin.

AB - Anthracene and related compounds function as lifetime-extending cofactors in the (mesotetraphenylporphine)MnIII chloride-catalyzed epoxidation of olefins. An experiment with a chiral porphyrin catalyst shows that enantioselectivity is preserved in the presence of the cofactor. Additional experiments show that (a) turnover number enhancement is greatest for the least reactive substrates, (b) derivatization of anthracene at the 9 and 10 positions largely eliminates the enhancement effect, and (c) anthracene is ultimately converted to anthraquinone. The origin of the observed enhancements is in the reaction of anthracene with the normally unreactive dimeric oxo-bridged form of the catalyst. This reaction, which produces anthraquinone, regenerates the catalytically active monomeric form of the manganese porphyrin.

UR - http://www.scopus.com/inward/record.url?scp=23244446998&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=23244446998&partnerID=8YFLogxK

U2 - 10.1021/ic0505596

DO - 10.1021/ic0505596

M3 - Article

VL - 44

SP - 5523

EP - 5529

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 15

ER -