Carbazole-based tridentate ligand, HCztBu(PyrH)2- {3,6-di(tert-butyl)-1,8-di(pyrazol-1-yl)-9H-carbazole} (L), was synthesized and complexed with various late transition metal salts resulting in four distinct L2MII complexes (M = Fe (1), Co (2), Ni (3), Zn (4)). X-ray crystallography revealed 1-4 adopt a slightly-distorted octahedral environment due to the two orthogonally coordinated N,N,N-donor ligands. Cyclic voltammograms (CVs) exhibit three quasi-reversible one-electron reduction events for 1 and 2, and two quasi-reversible one-electron reduction events for 3 and 4. Chemical oxidation of 1 and 2 using 1 equiv of ferrocinium hexafluorophosphate (Cp2FePF6) resulted in a metal center oxidation (1+ and 2+). Further oxidation of 1+, 2+, and 3 using 2 equiv tris(2,4-dibromophenyl)aminium hexachloroantimonate ([N(C6H3Br2-2,4)3]SbCl6) resulted in the believed ligand-oxidized products (13+, 23+, and 32+). Single crystal X-ray diffraction studies of 1+ and 2+ showed the presence of one PF6- counterion, while 13+, 23+, and 32+ indicate the presence of appropriate numbers of SbCl6 counterions, signifying successful oxidation. UV-visible spectroscopy shows the presence of the desired ligand-oxidized species upon addition of 2 equiv of [N(C6H3Br2-2,4)3]SbCl6 to 1+ and 2+.

Carbazole based non-innocent ligand metal complexes: Synthesis, characterization, and redox behavior

256th National Meeting (2018)

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