title: Activation of SO2 with [(η(5) -C5 Me5 )2 Ln(THF)2 ] (Ln=Eu, Yb) leading to dithionite and sulfinate complexes.
abstract: The reaction of decamethylytterbocene [(η(5) -C5 Me5 )2 Yb(THF)2 ] with SO2 at low temperature gave two new compounds, namely, the Yb(III) dithionite/sulfinate complex [{(η(5) -C5 Me5 )2 Yb(μ3 ,1κ(2) O(1,3) ,2κ(3) O(2,2',4) -S2 O4 )}2 {(η(5) -C5 Me5 )Yb(μ,1κO,2κO'-C5 Me5 SO2 )}2 ] (1) and the Yb(III) dithionite complex [{(η(5) -C5 Me5 )2 Yb}2 (μ,1κ(2) O(1,3) ,2κ(2) O(2,4) -S2 O4 )] (2). After extraction of 1, the mixture was heated to give the dinuclear tetrasulfinate complex [{(η(5) -C5 Me5 )Yb}2 (μ,κO,κO'-C5 Me5 SO2 )4 ] (3 a). In contrast, from the reaction of [(η(5) -C5 Me5 )2 Eu(THF)2 ] with SO2 only the tetrasulfinate complex [{(η(5) -C5 Me5 )Eu}2 (μ,κO,κO'-C5 Me5 SO2 )4 ] (3 b) was isolated. Two major reaction pathways were observed: 1) reductive coupling of two SO2 molecules to form the dithionite anion S2 O4 (2-) ; and 2) nucleophilic attack of one metallocene C5 Me5 ligand on the sulfur atom of SO2 . The compounds presented are the first dithionite and sulfinate complexes of the f-elements.
authors.affiliation: Institut für Anorganische Chemie, Karlsruher Institut für Technologie (KIT), Engesserstrasse 15, Geb. 30.45, 76131 Karlsruhe (Germany), Fax: (+49) 721-608-44854; G.A. Razuvaev Institute of Organometallic Chemistry, RAS, Tropinina str. 49, 603950 Nizhny Novgorod, (Russia).
authors.forename: Svetlana V
authors.initials: SV
authors.lastname: Klementyeva
authors.forename: Michael T
authors.initials: MT
authors.lastname: Gamer
authors.forename: Anna-Corina
authors.initials: AC
authors.lastname: Schmidt
authors.forename: Karsten
authors.initials: K
authors.lastname: Meyer
authors.forename: Sergey N
authors.initials: SN
authors.lastname: Konchenko
authors.forename: Peter W
authors.initials: PW
authors.lastname: Roesky
keywords: SO2 complexes; dithionite complexes; lanthanides; rare earths; reduction