Jump to main content
Jump to site search

Issue 1, 2013
Previous Article Next Article

Stepwise formation of organometallic macrocycles and triangular prisms containing 2,2′-bisbenzimidazole ligands

Author affiliations

Abstract

A series of organometallic macrocycles have been constructed by an efficient “bottom-up” assembly methodology at ambient temperature. Treatment of [Cp*MCl2]2 (1a: M = Ir, 1b: M = Rh) with pyrazine or 4,4′-bipyridine (bpy) (1 : 1; Cp* = pentamethylcyclopentadienyl) at room temperature resulted in the formation of binuclear complexes [Cp*MCl2]2(pyrazine) and [Cp*MCl2]2(bpy) (M = Ir or Rh), which were then further reacted with AgOTf (Tf = O2SCF3) and 2,2′-bisbenzimidazole ligand (BiBzIm). Four organometallic macrocyclic complexes formulated as [Cp*4Ir4(BiBzIm)2(pyrazine)2](OTf)4 (2a), [Cp*4Rh4(BiBzIm)2(pyrazine)2](OTf)4 (2b), [Cp*4Ir4(BiBzIm)2(bpy)2](OTf)4 (2c) and [Cp*4Rh4(BiBzIm)2(bpy)2](OTf)4 (2d) each bearing 2,2′-bisbenzimidazole ligand and the half-sandwich Ir, Rh fragments were finally obtained in good yields. In a similar process, if a rigid ligand L (3-pyridyl-bian) was used as the linker, two novel metallacycles (3a and 3b) which enchased a silver atom in the centre were obtained. Organometallic triangular prisms 4a were synthesized via methods similar to those of the rectangles. [Cp*IrCl2]2 reacted with tridentate ligand 2,4,6-tri(4-pyridyl)-1,3,5-triazine (tpt) to give the corresponding trinuclear complexes [Cp*IrCl2]3(tpt), then further reacted with AgOTf and 2,2′-bisbenzimidazole ligand, leading to the formation of the prism-like complexes formulated as [Cp*6M6(BiBzIm)6(tpt)2](OTf)6 (3a: M = Ir, 3b: M = Rh). All complexes were well characterized by 1H NMR and IR spectroscopy, as well as elemental analyses. The molecular structures of 2a, 2b, 2c, 3a, 3b and 4a were characterized by single-crystal X-ray crystallography. We found that the prism-like hexanuclear complexes 4a displayed interesting host–guest chemistry.

Graphical abstract: Stepwise formation of organometallic macrocycles and triangular prisms containing 2,2′-bisbenzimidazole ligands

Back to tab navigation
Please wait while Download options loads

Supplementary files

Publication details

The article was received on 27 Jun 2012, accepted on 12 Sep 2012, published on 13 Sep 2012 and first published online on 13 Sep 2012


Article type: Paper
DOI: 10.1039/C2DT31387A
Citation: Dalton Trans., 2013,42, 82-88
  •   Request permissions

    Stepwise formation of organometallic macrocycles and triangular prisms containing 2,2′-bisbenzimidazole ligands

    T. Wu, Y. Lin and G. Jin, Dalton Trans., 2013, 42, 82
    DOI: 10.1039/C2DT31387A

Search articles by author