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Bimetallic ruthenium–tin chemistry: Synthesis and molecular structure of arene ruthenium complexes containing trichlorostannyl ligands
Auteur(s)
Thai, Trieu-Tien
Shapovalov, Sergey S.
Pasynskii, Alexandr A.
Plasseraud, Laurent
Date de parution
2010
In
Journal of Organometallic Chemistry, Elsevier, 2010/695/3/409-414
Résumé
A series of neutral, anionic and cationic arene ruthenium complexes containing the trichlorostannyl ligand have been synthesised from SnCl<sub>2</sub> and the corresponding arene ruthenium dichloride dimers [(η<sup>6</sup>-arene)Ru(μ<sub>2</sub>-Cl)Cl]<sub>2</sub> (arene = C<sub>6</sub>H<sub>6</sub>, Pr<sup><i>i</i></sup>C<sub>6</sub>H<sub>4</sub>Me). While the reaction with triphenylphosphine and stannous chloride only gives the neutral mono(trichlorostannyl) complexes [(η<sup>6</sup>-C<sub>6</sub>H<sub>6</sub>)Ru(PPh<sub>3</sub>)(SnCl<sub>3</sub>)Cl] (<b>1</b>) and [(η<sup>6</sup>-Pr<sup><i>i</i></sup>C<sub>6</sub>H<sub>4</sub>Me)Ru(PPh<sub>3</sub>)(SnCl<sub>3</sub>)Cl] (<b>2</b>), the neutral di(trichlorostannyl) complex [(η<sup>6</sup>-Pr<sup><i>i</i></sup>C<sub>6</sub>H<sub>4</sub>Me)Ru(NCPh)(SnCl<sub>3</sub>)<sub>2</sub>] (<b>3</b>) could be obtained for the para-cymene derivative with benzonitrile as additional ligand. By contrast, the analogous reaction with the benzene derivative leads to a salt composed of the cationic mono(trichlorostannyl) complex [(η<sup>6</sup>-C<sub>6</sub>H<sub>6</sub>)Ru(NCPh)<sub>2</sub>(SnCl<sub>3</sub>)]<sup>+</sup> (<b>5</b>) and of the anionic tris(trichlorostannyl) complex [(η<sup>6</sup>-C<sub>6</sub>H<sub>6</sub>)Ru(SnCl<sub>3</sub>)<sub>3</sub>]<sup>−</sup> (<b>6</b>). On the other hand, [(η<sup>6</sup>-Pr<sup><i>i</i></sup>C<sub>6</sub>H<sub>4</sub>Me)Ru(μ<sub>2</sub>-Cl)Cl]<sub>2</sub> reacts with SnCl<sub>2</sub> and hexamethylenetetramine hydrochloride or 18-crown-6 to give the anionic di(trichlorostannyl) complex [(η<sup>6</sup>-Pr<sup><i>i</i></sup>C<sub>6</sub>H<sub>4</sub>Me)Ru(SnCl<sub>3</sub>)<sub>2</sub>Cl]<sup>−</sup> (<b>4</b>), isolated as the hexamethylenetetrammonium salt or the chloro-tin 18-crown-6 salt. The single-crystal X-ray structure analyses of <b>1</b>, <b>2</b>, [(CH<sub>2</sub>)<sub>6</sub>N<sub>4</sub>H][<b>4</b>], [(18-crown-6)SnCl][<b>4</b>] and [<b>5</b>][<b>6</b>] reveal for all complexes a <i>pseudo</i>-tetrahedral piano-stool geometry with ruthenium–tin bonds ranging from 2.56 (anionic complexes) to 2.60 Å (cationic complex).
Identifiants
Type de publication
journal article
