The Fascinating Flexibility and Coordination Modes of a Pentamethylene Connected Macrocyclic CNC Pincer Ligand

The coordination chemistry of an electron-rich macrocyclic CNC pincer-ligand consisting of two pentamethylene tethered N-heterocyclic carbene moieties on a carbazole backbone (bimca(C5)) is investigated by mainly NMR spectroscopy and X-ray crystal structure analysis. A bridging coordination mode is found for the lithium complex. With the larger and softer potassium ion, the ligand adopts a facial coordination mode and a polymeric structure by intermolecular potassium nitrogen interactions. The facial coordination is also confirmed at a Cp*Ru fragment, while C-H activation under dehydrogenation at the alkyl chain is observed upon reaction with [Ru(PPh3)(3)Cl-2]. In contrast, Pd(OAc)(2) reacts under C-H activation at the central carbon atom of the pentamethylene tether to an alkyl-pincer macrocycle.

Automated summary

The coordination chemistry of an electron-rich macrocyclic CNC pincer-ligand was studied using NMR spectroscopy and X-ray crystal structure analysis. It was found that the ligand exhibited bridging coordination with lithium, facial coordination with potassium, and C-H activation with metal complexes.