Activation of SO2 with [(η5‐C5Me5)2Ln(THF)2] (Ln=Eu,Yb) Leading to Dithionite and Sulfinate Complexes |
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| Authors: | Dr. Svetlana V. Klementyeva Dr. Michael T. Gamer Anna‐Corina Schmidt Prof. Dr. Karsten Meyer Prof. Dr. Sergey N. Konchenko Prof. Dr. Peter W. Roesky |
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| Affiliation: | 1. Institut für Anorganische Chemie, Karlsruher Institut für Technologie (KIT), Engesserstrasse 15, Geb. 30.45, 76131 Karlsruhe (Germany), Fax: (+49)?721‐608‐44854;2. G.A. Razuvaev Institute of Organometallic Chemistry, RAS, Tropinina str. 49, 603950 Nizhny Novgorod, (Russia);3. Friedrich‐Alexander University Erlangen‐Nürnberg (FAU), Department of Chemistry and Pharmacy, Inorganic Chemistry, Egerlandstrasse 1, 91058 Erlangen, (Germany), Fax: (+49)?9131 8527367;4. Nikolaev Institute of Inorganic Chemistry SB RAS, Prosp. Lavrentieva 3, 630090 Novosibirsk (Russia);5. Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk (Russia) |
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| Abstract: | The reaction of decamethylytterbocene [(η5‐C5Me5)2Yb(THF)2] with SO2 at low temperature gave two new compounds, namely, the YbIII dithionite/sulfinate complex [{(η5‐C5Me5)2Yb(μ3,1κ2O1,3,2κ3O2,2′,4‐S2O4)}2{(η5‐C5Me5)Yb(μ,1κO,2κO′‐C5Me5SO2)}2] ( 1 ) and the YbIII dithionite complex [{(η5‐C5Me5)2Yb}2(μ,1κ2O1,3,2κ2O2,4‐S2O4)] ( 2 ). After extraction of 1 , the mixture was heated to give the dinuclear tetrasulfinate complex [{(η5‐C5Me5)Yb}2(μ,κO,κO’‐C5Me5SO2)4] ( 3 a ). In contrast, from the reaction of [(η5‐C5Me5)2Eu(THF)2] with SO2 only the tetrasulfinate complex [{(η5‐C5Me5)Eu}2(μ,κO,κO’‐C5Me5SO2)4] ( 3 b ) was isolated. Two major reaction pathways were observed: 1) reductive coupling of two SO2 molecules to form the dithionite anion S2O42?; and 2) nucleophilic attack of one metallocene C5Me5 ligand on the sulfur atom of SO2. The compounds presented are the first dithionite and sulfinate complexes of the f‐elements. |
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| Keywords: | dithionite complexes lanthanides rare earths reduction SO2 complexes |
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