Isocyanide ligation at ruthenium(II) complexes with chelating tertiary amine and porphyrin ligands. Structural and electrochemical studies

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

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  • Fu-Wa Lee
  • Mei-Yuk Choi
  • Kung-Kai Cheung
  • Chi-Ming Che


Original languageEnglish
Pages (from-to)114-125
Journal / PublicationJournal of Organometallic Chemistry
Issue number1
Publication statusPublished - 31 Jan 2000
Externally publishedYes


Reaction of [Ru(Me3tacn)(PMe3)2(O2CCF 3)]PF6 with one equivalent of t-BuNC or 4-cyano-1-isocyano-2,6-diisopropylbenzene (L′) in refluxing 1,2-dichloroethane gave [Ru(Me3tacn)(PMe3)(t-BuNC)(O2CCF 3)]PF6 (1)·PF6 and [Ru(Me3tacn)(PMe3)(L′)(O2CCF 3)]PF6 (3)·PF6, respectively. In the presence of zinc amalgam, reactions of [Ru(Me3tacn)(H2O)2(O2CCF 3)](OTf)2, trans-[Ru(16-TMC)Cl2]Cl and cis-[Ru(2,2,2-tet-Me6)Cl2]PF6 with an excess of t-BuNC in 1,2-dichloroethane, followed by anion metathesis, afforded [Ru(Me3tacn)(t-BuNC)2(O2CCF 3)]PF6 (2)·PF6, trans-[Ru(16-TMC)(t-BuNC)2](ClO4)2 (4)·(ClO4)2 and cis-[Ru(2,2,2-tet-Me6)(t-BuNC)2](PF6) 2 (5)·(PF6)2, respectively. Treatment of [Ru(Por)(CO)(MeOH)] (Por=TPP, 4-MeO-TPP or 4-F-TPP) with an excess of t-BuNC or L′ gave [Ru(TPP)(t-BuNC)2] (6) or [Ru(4-MeO-TPP)(L′)2] (7) and [Ru(4-F-TPP)(L′)2] (8), respectively. 1·PF6-5·(PF6)2 display a quasi-reversible Ru(III/II) couple at potentials ranging from +0.65 to +1.42 V vs. FeCp2 +/0. The E1/2(RuIII/II) of 5·(PF6)2 (+1.42 V vs. FeCp2 +/0) is notably high compared with that of 4·(ClO4)2 (+0.65 V), reflecting the strong π-back-bonding in the cis-bis(tert-butyl isocyanide)ruthenium(II) complex. Irrespective of the overall charge, the cationic complex 4 and the neutral complexes 6-8 all exhibit a virtually linear RNC-Ru-CNR moiety. © 2000 Elsevier Science S.A.

Research Area(s)

  • Crystal structures, Electrochemistry, Isocyanide complexes, Porphyrins, Ruthenium, Tertiary amine

Citation Format(s)