Catalysts for monooxygenations made from polyoxometalate: An iron(V)-oxo derivative of the Lindqvist anion

Etienne Derat, Devesh Kumar, Ronny Neumann, Sason Shaik

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

This work uses density functional calculations to design a new high-valent Fe(V)=O catalyst [Mo5O18Fe=O]3-, which is based on the Lindqvist polyoxometalate (Mo6O19 2-). Because the parent species is stable to oxidative conditions, one may assume that the newly proposed iron-oxo species will be stable, too. The calculated Mössbauer spectroscopic data may be helpful toward an eventual identification of the species. The calculations of C-H hydroxylation and C=C epoxidation of propene show that, if made, [Mo5O18Fe=O] 3- should be a potent oxidant that will be subject to strong solvent effect. Moreover, the Lindqvist catalyst leads to an intriguing result; the reaction that starts along an epoxidation pathway with C=C activation ends with a C-H hydroxylation product (46) due to rearrangement on the catalyst. The origins of this result are analyzed in terms of the structure of the catalyst and the electronic requirements for conversion of an epoxidation intermediate to a hydroxylation product. Thus, if made, the [Mo 5O18Fe=O]3 will be a selective C-H hydroxylation reagent.

Original languageEnglish
Pages (from-to)8655-8663
Number of pages9
JournalInorganic Chemistry
Volume45
Issue number21
DOIs
Publication statusPublished - Oct 16 2006

Fingerprint

Hydroxylation
epoxidation
Anions
Epoxidation
anions
Derivatives
iron
catalysts
Catalysts
products
Oxidants
Density functional theory
reagents
Iron
Chemical activation
activation
requirements
polyoxometalate I
perferryl iron
electronics

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Catalysts for monooxygenations made from polyoxometalate : An iron(V)-oxo derivative of the Lindqvist anion. / Derat, Etienne; Kumar, Devesh; Neumann, Ronny; Shaik, Sason.

In: Inorganic Chemistry, Vol. 45, No. 21, 16.10.2006, p. 8655-8663.

Research output: Contribution to journalArticle

@article{443a43463d2a4699a700b30d9e910920,
title = "Catalysts for monooxygenations made from polyoxometalate: An iron(V)-oxo derivative of the Lindqvist anion",
abstract = "This work uses density functional calculations to design a new high-valent Fe(V)=O catalyst [Mo5O18Fe=O]3-, which is based on the Lindqvist polyoxometalate (Mo6O19 2-). Because the parent species is stable to oxidative conditions, one may assume that the newly proposed iron-oxo species will be stable, too. The calculated M{\"o}ssbauer spectroscopic data may be helpful toward an eventual identification of the species. The calculations of C-H hydroxylation and C=C epoxidation of propene show that, if made, [Mo5O18Fe=O] 3- should be a potent oxidant that will be subject to strong solvent effect. Moreover, the Lindqvist catalyst leads to an intriguing result; the reaction that starts along an epoxidation pathway with C=C activation ends with a C-H hydroxylation product (46) due to rearrangement on the catalyst. The origins of this result are analyzed in terms of the structure of the catalyst and the electronic requirements for conversion of an epoxidation intermediate to a hydroxylation product. Thus, if made, the [Mo 5O18Fe=O]3 will be a selective C-H hydroxylation reagent.",
author = "Etienne Derat and Devesh Kumar and Ronny Neumann and Sason Shaik",
year = "2006",
month = "10",
day = "16",
doi = "10.1021/ic0610435",
language = "English",
volume = "45",
pages = "8655--8663",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "21",

}

TY - JOUR

T1 - Catalysts for monooxygenations made from polyoxometalate

T2 - An iron(V)-oxo derivative of the Lindqvist anion

AU - Derat, Etienne

AU - Kumar, Devesh

AU - Neumann, Ronny

AU - Shaik, Sason

PY - 2006/10/16

Y1 - 2006/10/16

N2 - This work uses density functional calculations to design a new high-valent Fe(V)=O catalyst [Mo5O18Fe=O]3-, which is based on the Lindqvist polyoxometalate (Mo6O19 2-). Because the parent species is stable to oxidative conditions, one may assume that the newly proposed iron-oxo species will be stable, too. The calculated Mössbauer spectroscopic data may be helpful toward an eventual identification of the species. The calculations of C-H hydroxylation and C=C epoxidation of propene show that, if made, [Mo5O18Fe=O] 3- should be a potent oxidant that will be subject to strong solvent effect. Moreover, the Lindqvist catalyst leads to an intriguing result; the reaction that starts along an epoxidation pathway with C=C activation ends with a C-H hydroxylation product (46) due to rearrangement on the catalyst. The origins of this result are analyzed in terms of the structure of the catalyst and the electronic requirements for conversion of an epoxidation intermediate to a hydroxylation product. Thus, if made, the [Mo 5O18Fe=O]3 will be a selective C-H hydroxylation reagent.

AB - This work uses density functional calculations to design a new high-valent Fe(V)=O catalyst [Mo5O18Fe=O]3-, which is based on the Lindqvist polyoxometalate (Mo6O19 2-). Because the parent species is stable to oxidative conditions, one may assume that the newly proposed iron-oxo species will be stable, too. The calculated Mössbauer spectroscopic data may be helpful toward an eventual identification of the species. The calculations of C-H hydroxylation and C=C epoxidation of propene show that, if made, [Mo5O18Fe=O] 3- should be a potent oxidant that will be subject to strong solvent effect. Moreover, the Lindqvist catalyst leads to an intriguing result; the reaction that starts along an epoxidation pathway with C=C activation ends with a C-H hydroxylation product (46) due to rearrangement on the catalyst. The origins of this result are analyzed in terms of the structure of the catalyst and the electronic requirements for conversion of an epoxidation intermediate to a hydroxylation product. Thus, if made, the [Mo 5O18Fe=O]3 will be a selective C-H hydroxylation reagent.

UR - http://www.scopus.com/inward/record.url?scp=33750305346&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33750305346&partnerID=8YFLogxK

U2 - 10.1021/ic0610435

DO - 10.1021/ic0610435

M3 - Article

C2 - 17029376

AN - SCOPUS:33750305346

VL - 45

SP - 8655

EP - 8663

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 21

ER -