The RuIV=O-catalyzed sulfoxidation: a gated mechanism where O to S linkage isomerization switches between different efficiencies
Two Ru(IV)=O catalysts with either a pentadentate bispidine ligand L(1) or a bidentate pyrazolate L(2)/terpy L(3) combination of ligands have very different efficiencies as oxygen transfer catalysts for the selective oxidation of sulfides to sulfoxides: the [Ru(II)(L(1))(solvent)](2+)/iodosyl benzen...
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| Main Authors: | , , , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
2010
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| In: |
Dalton transactions
Year: 2010, Volume: 39, Issue: 13, Pages: 1-33 |
| ISSN: | 1477-9234 |
| DOI: | 10.1039/b924614b |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1039/b924614b Verlag, lizenzpflichtig, Volltext: http://xlink.rsc.org/?DOI=b924614b 
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| Author Notes: | Jordi Benet-Buchholz, Peter Comba, Antoni Llobet, Stephan Roeser, Prabha Vadivelu and Sebastian Wiesner |
| Summary: | Two Ru(IV)=O catalysts with either a pentadentate bispidine ligand L(1) or a bidentate pyrazolate L(2)/terpy L(3) combination of ligands have very different efficiencies as oxygen transfer catalysts for the selective oxidation of sulfides to sulfoxides: the [Ru(II)(L(1))(solvent)](2+)/iodosyl benzene system has an initial TOF of approx. 40 h(-1) and quantitative yield, with [Ru(II)(L(2))(L(3))(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 Ru(II) sulfoxide product complex, and this may partially switch off the catalytic cycle for the L(2)/L(3)-based catalyst. It emerges that the reasons for the reduced efficiency in the case of the L(2)/L(3), in comparison with the L(1)-based catalyst, are a more efficient linkage isomerization, a more stable S-bonded, in comparison with the O-bonded, Ru(II)-based isomer, and inefficient ligand exchange in the product (hydrolysis produces the free sulfoxide and the Ru(II) precatalyst). These interpretations are qualitatively in good agreement with preliminary DFT-based data. |
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| Item Description: | Im Titel ist "IV" hochgestellt Gesehen am 12.01.2023 |
| Physical Description: | Online Resource |
| ISSN: | 1477-9234 |
| DOI: | 10.1039/b924614b |