Functionalized arene-ruthenium(ii) complexes: dangling vs. tethering side chainElectronic supplementary information (ESI) available: Synthesis of complex 5c[SbF6]; CIF file giving crystallographic data for compounds 2[SbF6]2, 3[SbF6] and 5a[SbF6]; details on the chemical behavior of 1b and 4b in water; Cartesian coordinates and total energies of 1M and 4M. CCDC 908513, 908514 and 908515. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c3dt33051f

• Main Authors: Lastra-Barreira, Beatriz, Díez, Josefina, Crochet, Pascale, Fernández, Israel
• Format: Article
• Language: English
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c3dt33051f

The reactivity of compounds [RuCl 2 (η 6 -C 6 H 5 OCH 2 CH 2 OH)(L)] (L = phosphine or phosphite) towards the chloride abstractor AgSbF 6 has been investigated. Thus, the treatment of the triphenylphosphite complex [RuCl 2 (η 6 -C 6 H 5 OCH 2 CH 2 OH){P(OPh) 3 }] with one equivalent of AgSbF 6 gave rise to the formation of the dinuclear dichloro-bridged species [{Ru(μ-Cl)(η 6 -C 6 H 5 OCH 2 CH 2 OH){P(OPh) 3 }} 2 ] 2+ as the hexafluoroantimonate salt. On the other hand, the triphenylphosphine analog [RuCl 2 (η 6 -C 6 H 5 OCH 2 CH 2 OH)(PPh 3 )] led, under the same experimental conditions, to the di-ruthenium derivative [{RuCl(η 6 -C 6 H 5 OCH 2 CH 2 OH)(PPh 3 )} 2 (μ-Cl)][SbF 6 ] containing only one Cl-bridge. In sharp contrast, treatment of precursors [RuCl 2 (η 6 -C 6 H 5 CH 2 CH 2 CH 2 OH)(L)] (L = P(OPh) 3 , PPh 3 , P(OEt) 3 ) with AgSbF 6 resulted in the clean formation of the tethered compounds [RuCl{η 6 :κ 1 ( O )-C 6 H 5 CH 2 CH 2 CH 2 OH}(L)][SbF 6 ]. The differences in reactivity observed have been rationalized by theoretical calculations. The reactivity of different functionalized arene-ruthenium( ii ) complexes has been studied and rationalized.