(Mesitylene)ruthenium π-complexes with benzo-15-crown-5 and dibenzo-18-crown-6

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Author(s)

  • Dmitry S. Perekalin
  • Valentin V. Novikov
  • Konstantin A. Lyssenko
  • Maddalena Corsini
  • Piero Zanello
  • Alexander R. Kudinov

Detail(s)

Original languageEnglish
Pages (from-to)1200-1204
Journal / PublicationJournal of Organometallic Chemistry
Volume695
Issue number8
Online published1 Feb 2010
Publication statusPublished - 15 Apr 2010
Externally publishedYes

Abstract

The reactions of benzo-15-crown-5 and dibenzo-18-crown-6 with 1 equiv. of [(mes)Ru(MeNO2)3]2+ (mes = 1,3,5-C6H3Me3) give the mononuclear complexes [(mes)Ru(η6-benzo-15-crown-5)]2+ (1) and [(mes)Ru(η6-dibenzo-18-crown-6)]2+ (2) in 50% yield. Similar reaction with 2 equiv. of [(mes)Ru(MeNO2)3]2+ produces the dinuclear complex [(μ-η66-dibenzo-18-crown-6)Ru2(mes)2]4+ (3) in 96% yield as a 2:3 mixture of cis- and trans-isomers. Structures of 2(OTf)2 and trans-3(OTf)4 were confirmed by X-ray diffraction. The NMR titration showed that mononuclear dications 1 and 2 bind Na+ ion less effective (Ka = 600 and 250 M-1) than free benzo-15-crown-5 and dibenzo-18-crown-6 (Ka = 2 × 105 and 5 × 106 M-1). The dinuclear tetracation 3 does not bind Na+ within measurable limits of NMR titration method. The electrochemical behaviour of complexes 1-3 was studied in propylene carbonate solution. They exhibit a partially chemically reversible Ru(II)/Ru(I) reduction, which in the case of the dinuclear complex 3 proceeds through two slightly separated steps. The redox activity of the complexes is substantially unaffected by the presence of sodium ion. © 2010 Elsevier B.V. All rights reserved.

Research Area(s)

  • Crown ethers, Electrochemistry, NMR titration, Ruthenium, Sandwich complexes

Citation Format(s)

(Mesitylene)ruthenium π-complexes with benzo-15-crown-5 and dibenzo-18-crown-6. / Perekalin, Dmitry S.; Babak, Maria V.; Novikov, Valentin V. et al.

In: Journal of Organometallic Chemistry, Vol. 695, No. 8, 15.04.2010, p. 1200-1204.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review