Oxidative reactions of “half-sandwich” ruthenium compounds: formation of cationic nitrosyl ruthenium(II) derivatives
Identifieur interne : 007D31 ( Main/Merge ); précédent : 007D30; suivant : 007D32Oxidative reactions of “half-sandwich” ruthenium compounds: formation of cationic nitrosyl ruthenium(II) derivatives
Auteurs : Pietro Diversi [Italie] ; Marco Fontani [Italie] ; Melania Fuligni [Italie] ; Franco Laschi [Italie] ; Simona Matteoni [Italie] ; Calogero Pinzino [Italie] ; Piero Zanello [Italie]Source :
- Journal of Organometallic Chemistry [ 0022-328X ] ; 2001.
Descripteurs français
- Wicri :
- topic : électrochimie.
English descriptors
Abstract
The electrochemical behaviour of the ruthenium(II) alkyl complexes [Ru(Me)Cp*(L)2] (Cp*=η5-C5Me5; L=PMe3 2a, PMe2Ph 2b), [Ru(CH2CMe3)Cp*(PMe3)2] (3a), and the related [Ru(Me)Cp(PPh3)2] (4d) (Cp=η5-C5H5) in CH2Cl2 involves a one-electron process, yielding the corresponding ruthenium(III) paramagnetic cations, as shown by coupled electrochemical–EPR studies. Compounds 2–4 are oxidised by [FeCp2]+ in benzene to unidentified paramagnetic products which may decompose giving the corresponding alkane. The Cp* compounds react with NOBF4 affording the monocationic alkylnitrosyl derivatives [Ru(R)Cp*(NO)(L)]BF4 (R=Me; L=PMe3 7a, PMe2Ph 7b. R=CH2CMe3; L=PMe3) and, when in excess of NO+, the ruthenium(II) dicationic complexes [RuCp*(NO)(L)2](BF4)2 (L=PMe3 5a, PMe2Ph 5b). The chloro complexes [Ru(Cl)Cp*(L)2] (L=PMe3 1a, PMe2Ph 1b, PPh3 1d) react analogously with NO+ to give [Ru(Cl)Cp*(NO)(L)]BF4 (L=PMe3 6a, PMe2Ph 6b, PPh3 6d) and [RuCp*(NO)(L)2](BF4)2 (L=PMe3 5a, PMe2Ph 5b). In contrast [Ru(Me)Cp(PPh3)2] gives only [Ru(Me)Cp(NO)(PPh3)]BF4. EPR spectroscopy suggests that these nitrosylation reactions are also oxidative in character proceeding through ruthenium(III) intermediates.
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DOI: 10.1016/S0022-328X(01)00680-5
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scheme="Wicri" type="topic" xml:lang="fr"><term>électrochimie</term></keywords></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">The electrochemical behaviour of the ruthenium(II) alkyl complexes [Ru(Me)Cp*(L)2] (Cp*=η5-C5Me5; L=PMe3 2a, PMe2Ph 2b), [Ru(CH2CMe3)Cp*(PMe3)2] (3a), and the related [Ru(Me)Cp(PPh3)2] (4d) (Cp=η5-C5H5) in CH2Cl2 involves a one-electron process, yielding the corresponding ruthenium(III) paramagnetic cations, as shown by coupled electrochemical–EPR studies. Compounds 2–4 are oxidised by [FeCp2]+ in benzene to unidentified paramagnetic products which may decompose giving the corresponding alkane. The Cp* compounds react with NOBF4 affording the monocationic alkylnitrosyl derivatives [Ru(R)Cp*(NO)(L)]BF4 (R=Me; L=PMe3 7a, PMe2Ph 7b. R=CH2CMe3; L=PMe3) and, when in excess of NO+, the ruthenium(II) dicationic complexes [RuCp*(NO)(L)2](BF4)2 (L=PMe3 5a, PMe2Ph 5b). The chloro complexes [Ru(Cl)Cp*(L)2] (L=PMe3 1a, PMe2Ph 1b, PPh3 1d) react analogously with NO+ to give [Ru(Cl)Cp*(NO)(L)]BF4 (L=PMe3 6a, PMe2Ph 6b, PPh3 6d) and [RuCp*(NO)(L)2](BF4)2 (L=PMe3 5a, PMe2Ph 5b). In contrast [Ru(Me)Cp(PPh3)2] gives only [Ru(Me)Cp(NO)(PPh3)]BF4. EPR spectroscopy suggests that these nitrosylation reactions are also oxidative in character proceeding through ruthenium(III) intermediates.</div></front></TEI></record>Pour manipuler ce document sous Unix (Dilib)
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