Activation of SO2 with [(η(5) -C5 Me5 )2 Ln(THF)2 ] (Ln=Eu, Yb) leading to dithionite and sulfinate complexes

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.