Issue 42, 2011
From the journal:

Dalton Transactions

A combined experimental and computational study on the sulfoxidation by high-valent iron bispidine complexes†

Madhavan Jaccob,ab   Peter Comba,*a   Martin Maurer,a   Prabha Vadivelua  and  Ponnambalam Venuvanalingamb  

* Corresponding authors

a Universität Heidelberg, Anorganisch-Chemisches Institut, INF 270, Heidelberg, Germany
E-mail: peter.comba@aci.uni-heidelberg.de
Fax: +49-6226-546617

b Theoretical and Computational Chemistry Laboratory, School of Chemistry, Bharathidasan University, Tiruchirappalli, Tamil Nadu, India

Abstract

Iron-bispidine complexes are efficient catalysts for the oxidation of thioanisole to phenylmethylsulfoxide with iodosylbenzene as oxidant. With the tetradentate bispidine ligand L1 (L1 = 2,4-pyridyl-3,7-diazabicyclo[3.3.1]nonane)) the catalytic efficiency is smaller than with the pentadentate bispidine ligand L2 (L2 = 2,4-pyridyl-7-(pyridine-2-ylmethyl)-3,7-diazabicyclo[3.3.1]nonane)). Based on the redox potentials (iron complexes with L1 are stronger oxidants than with L2) and known efficiencies in catalytic olefin oxidation and C–H activation reactions, the expectations were different. A DFT-based analysis is used to explain the apparent contradiction, and this is based on differences in the electronic ground states of the ferryl complexes as well as in the oxygen transfer transition states.

Graphical abstract: A combined experimental and computational study on the sulfoxidation by high-valent iron bispidine complexes

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Article information

DOI
https://doi.org/10.1039/C1DT11533B
Article type
Paper
Submitted
15 Aug 2011
Accepted
06 Sep 2011
First published
29 Sep 2011

Dalton Trans., 2011,40, 11276-11281

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A combined experimental and computational study on the sulfoxidation by high-valent iron bispidine complexes

M. Jaccob, P. Comba, M. Maurer, P. Vadivelu and P. Venuvanalingam, Dalton Trans., 2011, 40, 11276 DOI: 10.1039/C1DT11533B

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