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Activation of SO 2 with [(η 5 ‐C 5 Me 5 ) 2 Ln(THF) 2 ] (Ln=Eu, Yb) Leading to Dithionite and Sulfinate Complexes
Author(s) -
Klementyeva Svetlana V.,
Gamer Michael T.,
Schmidt AnnaCorina,
Meyer Karsten,
Konchenko Sergey N.,
Roesky Peter W.
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201404399
Subject(s) - dithionite , chemistry , sulfur , crystallography , ligand (biochemistry) , inorganic chemistry , stereochemistry , biochemistry , receptor , organic chemistry , enzyme
The reaction of decamethylytterbocene [(η 5 ‐C 5 Me 5 ) 2 Yb(THF) 2 ] with SO 2 at low temperature gave two new compounds, namely, the Yb III dithionite/sulfinate complex [{(η 5 ‐C 5 Me 5 ) 2 Yb(μ 3 ,1κ 2 O 1,3 ,2κ 3 O 2,2′,4 ‐S 2 O 4 )} 2 {(η 5 ‐C 5 Me 5 )Yb(μ,1κO,2κO′‐C 5 Me 5 SO 2 )} 2 ] ( 1 ) and the Yb III dithionite complex [{(η 5 ‐C 5 Me 5 ) 2 Yb} 2 (μ,1κ 2 O 1,3 ,2κ 2 O 2,4 ‐S 2 O 4 )] ( 2 ). After extraction of 1 , the mixture was heated to give the dinuclear tetrasulfinate complex [{(η 5 ‐C 5 Me 5 )Yb} 2 (μ,κO,κO’‐C 5 Me 5 SO 2 ) 4 ] ( 3 a ). In contrast, from the reaction of [(η 5 ‐C 5 Me 5 ) 2 Eu(THF) 2 ] with SO 2 only the tetrasulfinate complex [{(η 5 ‐C 5 Me 5 )Eu} 2 (μ,κO,κO’‐C 5 Me 5 SO 2 ) 4 ] ( 3 b ) was isolated. Two major reaction pathways were observed: 1) reductive coupling of two SO 2 molecules to form the dithionite anion S 2 O 4 2− ; and 2) nucleophilic attack of one metallocene C 5 Me 5 ligand on the sulfur atom of SO 2 . The compounds presented are the first dithionite and sulfinate complexes of the f‐elements.