Catalytically active supramolecular porphyrin boxes: Acceleration of the methanolysis of phosphate triesters via a combination of increased local nucleophilicity and reactant encapsulation

Byungman Kang; Josh W. Kurutz; Kyoung Tae Youm; Ryan K. Totten; Joseph T. Hupp; Sonbinh T. Nguyen

doi:10.1039/c2sc00950a

Catalytically active supramolecular porphyrin boxes: Acceleration of the methanolysis of phosphate triesters via a combination of increased local nucleophilicity and reactant encapsulation

Byungman Kang, Josh W. Kurutz, Kyoung Tae Youm, Ryan K. Totten, Joseph T. Hupp^*, Sonbinh T. Nguyen

^*Corresponding author for this work

Chemistry

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42 Scopus citations

Abstract

Box-like tetrakis(metalloporphyrin) supramolecular assemblies possessing Zn and Al metal sites can catalyze the methanolysis of phosphate triesters with a high rate enhancement, up to 430 times faster than the uncatalyzed reaction. Mechanistic studies suggest that the observed rate enhancement can be attributed to a high local concentration of methoxide ion that operates in concert with a solvophobically driven encapsulation of substrates by the porphyrinic assembly.

Original language	English (US)
Pages (from-to)	1938-1944
Number of pages	7
Journal	Chemical Science
Volume	3
Issue number	6
DOIs	https://doi.org/10.1039/c2sc00950a
State	Published - Jun 2012

ASJC Scopus subject areas

General Chemistry

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title = "Catalytically active supramolecular porphyrin boxes: Acceleration of the methanolysis of phosphate triesters via a combination of increased local nucleophilicity and reactant encapsulation",

abstract = "Box-like tetrakis(metalloporphyrin) supramolecular assemblies possessing Zn and Al metal sites can catalyze the methanolysis of phosphate triesters with a high rate enhancement, up to 430 times faster than the uncatalyzed reaction. Mechanistic studies suggest that the observed rate enhancement can be attributed to a high local concentration of methoxide ion that operates in concert with a solvophobically driven encapsulation of substrates by the porphyrinic assembly.",

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year = "2012",

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doi = "10.1039/c2sc00950a",

language = "English (US)",

volume = "3",

pages = "1938--1944",

journal = "Chemical Science",

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publisher = "Royal Society of Chemistry",

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Catalytically active supramolecular porphyrin boxes: Acceleration of the methanolysis of phosphate triesters via a combination of increased local nucleophilicity and reactant encapsulation. / Kang, Byungman; Kurutz, Josh W.; Youm, Kyoung Tae et al.
In: Chemical Science, Vol. 3, No. 6, 06.2012, p. 1938-1944.

Research output: Contribution to journal › Article › peer-review

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AU - Kang, Byungman

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AU - Youm, Kyoung Tae

AU - Totten, Ryan K.

AU - Hupp, Joseph T.

AU - Nguyen, Sonbinh T.

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AB - Box-like tetrakis(metalloporphyrin) supramolecular assemblies possessing Zn and Al metal sites can catalyze the methanolysis of phosphate triesters with a high rate enhancement, up to 430 times faster than the uncatalyzed reaction. Mechanistic studies suggest that the observed rate enhancement can be attributed to a high local concentration of methoxide ion that operates in concert with a solvophobically driven encapsulation of substrates by the porphyrinic assembly.

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Catalytically active supramolecular porphyrin boxes: Acceleration of the methanolysis of phosphate triesters via a combination of increased local nucleophilicity and reactant encapsulation

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