Related Experiment Video
Updated: May 20, 2026

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
1,12-diazaperylene and 2,11-dialkylated-1,12-diazaperylene iridium(III) complexes [Ir(C^N)2(N^N)]PF6: new
Stefan Kammer1, Ines Starke, Andreas Pietrucha
1Universität Potsdam, Institut für Chemie, Anorganische Chemie, Potsdam, Germany.
Abstract:
A series of new monocationic iridium(III) complexes [Ir(C^N)(2)(N^N)]PF(6) with "large-surface"α,α'-diimin ligands N^N (dap = 1,12-diazaperylene, dmedap = 2,11-dimethyl-1,12-diazaperylene, dipdap = 2,11-diisopropyl-1,12-diazaperylene) and different cyclometalating ligands C^N (piq = 1-phenylisoquinoline, bzq = benzo[h]quinoline, ppz = 1-phenylpyrazole, thpy = 2-(2-thienyl)pyridine, ppy = 2-phenylpyridine, meppy = 2-(4-methylphenyl)pyridine, dfppy = 2-(2,4-difluorophenyl)pyridine) were synthesized. The solid structures of the complexes [Ir(piq)(2)(dap)]PF(6), [Ir(bzq)(2)(dap)]PF(6), [Ir(ppy)(2)(dipdap)]PF(6), [Ir(piq)(2)(dmedap)]PF(6), [Ir(ppy)(2)(dap)]PF(6) and [Ir(ppz)(2)(dap)]PF(6) are reported. In [Ir(piq)(2)(dap)]PF(6), the dap ligand and one of the piq ligands of each cationic complex are involved in π-π stacking interactions forming supramolecular channels running along the crystallographic c axis. In the crystalline [Ir(bzq)(2)(dap)]PF(6)π-π stacking interactions between the metal complexes lead to the formation of a 2D layer structure. In addition, CH-π interactions were found in all compounds, which are what stabilizes the solid structure. In particular, a significant number of them were found in [Ir(piq)(2)(dap)]PF(6) and [Ir(bzq)(2)(dap)]PF(6). The crystal structures of [Ir(ppy)(2)(dipdap)]PF(6) and [Ir(ppy)(2)(dmedap)]PF(6) are also presented, being the first examples of bis-cyclometalated iridium(iii) complexes with phenanthroline-type α,α'-diimin ligands bearing bulky alkyl groups in the neighbourhood of the N-donor atoms. These ligands implicate a distorted octahedral coordination geometry that in turn destabilized the Ir-N(N^N) bonds. The new iridium(iii) complexes are not luminescent. All compounds show an electrochemically irreversible anodic peak between 1.15 and 1.58 V, which is influenced by the different cyclometalated ligands. All of the new complexes show two reversible successive one-electron "large-surface" ligand-centred reductions around -0.70 V and -1.30 V. Electrospray ionisation mass spectrometry (ESI-MS) and collision induced decomposition (CID) measurements were used to investigate the stability of the new complexes. Thereby, the stability agreed well with the order of the Ir-N(N^N) bond lengths.
More Related Videos
14:11Synthesis of pH Dependent Pyrazole, Imidazole, and Isoindolone Dipyrrinone Fluorophores using a Claisen-Schmidt Condensation Approach
Published on: June 10, 2021
10:52Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Related Concept Videos
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
Diazonium Group Substitution: –OH and –H
Aryldiazonium Salts to Azo Dyes: Diazo Coupling
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
Coordination Number and Geometry