Issue 13, 2010
From the journal:

Dalton Transactions

The RuIV[double bond, length as m-dash]O-catalyzed sulfoxidation: a gated mechanism where O to S linkage isomerization switches between different efficiencies†

Jordi Benet-Buchholz,a   Peter Comba,*b   Antoni Llobet,*a   Stephan Roeser,a   Prabha Vadivelub  and  Sebastian Wiesnerb  

* Corresponding authors

a Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, Spain

b Universität Heidelberg, Anorganisch-Chemisches Institut, INF 270, Germany
E-mail: peter.comba@aci.uni-heidelberg.de
Fax: +49-6221-546617

Abstract

Two RuIV[double bond, length as m-dash]O catalysts with either a pentadentate bispidine ligand L1 or a bidentate pyrazolate L2/terpy L3 combination of ligands have very different efficiencies as oxygen transfer catalysts for the selective oxidation of sulfides to sulfoxides: the [RuII(L1)(solvent)]2+/iodosyl benzene system has an initial TOF of approx. 40 h−1 and quantitative yield, with [RuII(L2)(L3)(solvent)]+ the initial TOF is approx. 12 h−1 with a maximum yield of approx. 60%. By experiment (cyclovoltametry) it is shown that there is S- to O-linkage isomerization of the RuII sulfoxide product complex, and this may partially switch off the catalytic cycle for the L2/L3-based catalyst. It emerges that the reasons for the reduced efficiency in the case of the L2/L3, in comparison with the L1-based catalyst, are a more efficient linkage isomerization, a more stable S-bonded, in comparison with the O-bonded, RuII-based isomer, and inefficient ligand exchange in the product (hydrolysis produces the free sulfoxide and the RuII precatalyst). These interpretations are qualitatively in good agreement with preliminary DFT-based data.

Graphical abstract: The RuIV [[double bond, length as m-dash]] O-catalyzed sulfoxidation: a gated mechanism where O to S linkage isomerization switches between different efficiencies

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Article information

DOI
https://doi.org/10.1039/B924614B
Article type
Paper
Submitted
23 Nov 2009
Accepted
22 Jan 2010
First published
16 Feb 2010

Dalton Trans., 2010,39, 3315-3320

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The RuIV[double bond, length as m-dash]O-catalyzed sulfoxidation: a gated mechanism where O to S linkage isomerization switches between different efficiencies

J. Benet-Buchholz, P. Comba, A. Llobet, S. Roeser, P. Vadivelu and S. Wiesner, Dalton Trans., 2010, 39, 3315 DOI: 10.1039/B924614B

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