Activation of SO2 with [(η5‐C5Me5)2Ln(THF)2] (Ln=Eu, Yb) Leading to Dithionite and Sulfinate Complexes. Issue 42 (4th September 2014)

• Record Type: Journal Article
• Authors: Klementyeva, Svetlana V.; Gamer, Michael T.; Schmidt, Anna‐Corina; Meyer, Karsten; Konchenko, Sergey N.; Roesky, Peter W.
• Is Part Of: Chemistry. Volume 20:Issue 42(2014)
• Page Start: 13497
• Page End: 13500
• Publication Date: 2014-09-04
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201404399
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The reaction of decamethylytterbocene [(η<sup>5</sup>‐C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>Yb(THF)<sub>2</sub>] with SO<sub>2</sub> at low temperature gave two new compounds, namely, the Yb<sup>III</sup> dithionite/sulfinate complex [{(η<sup>5</sup>‐C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>Yb(μ<sub>3</sub>, 1κ<sup>2</sup>O<sup>1, 3</sup>, 2κ<sup>3</sup>O<sup>2, 2′, 4</sup>‐S<sub>2</sub>O<sub>4</sub>)}<sub>2</sub>{(η<sup>5</sup>‐C<sub>5</sub>Me<sub>5</sub>)Yb(μ, 1κO, 2κO′‐C<sub>5</sub>Me<sub>5</sub>SO<sub>2</sub>)}<sub>2</sub>] (<bold>1</bold>) and the Yb<sup>III</sup> dithionite complex [{(η<sup>5</sup>‐C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>Yb}<sub>2</sub>(μ, 1κ<sup>2</sup>O<sup>1, 3</sup>, 2κ<sup>2</sup>O<sup>2, 4</sup>‐S<sub>2</sub>O<sub>4</sub>)] (<bold>2</bold>). After extraction of <bold>1</bold>, the mixture was heated to give the dinuclear tetrasulfinate complex [{(η<sup>5</sup>‐C<sub>5</sub>Me<sub>5</sub>)Yb}<sub>2</sub>(μ, κO, κO'‐C<sub>5</sub>Me<sub>5</sub>SO<sub>2</sub>)<sub>4</sub>] (<bold>3 a</bold>). In contrast, from the reaction of [(η<sup>5</sup>‐C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>Eu(THF)<sub>2</sub>] with SO<sub>2</sub> only the tetrasulfinate complex [{(η<sup>5</sup>‐C<sub>5</sub>Me<sub>5</sub>)Eu}<sub>2</sub>(μ, κO, κO'‐C<sub>5</sub>Me<sub>5</sub>SO<sub>2</sub>)<sub>4</sub>] (<bold>3 b</bold>) was isolated. Two major reaction pathways were observed: 1) reductive coupling of two SO<sub>2</sub> molecules to form the dithionite anion S<sub>2</sub>O<sub>4</sub><sup>2−</sup>; and 2) nucleophilic attack of one metallocene C<sub>5</sub>Me<sub>5</sub> ligand on the sulfur atom of SO<sub>2</sub>. The compounds presented are the first dithionite and sulfinate complexes of the f‐elements.</p> </abstract>