Metal-ligand interactions in a redox active ligand system. Electrochemistry and spectroscopy of [M(dipyvd)2]n+ (M=Zn, Ni, n=0, 1, 2)

Reaction of nickel and zinc triflates with the tridentate leucoverdazyl 1-isopropyl-3,5-di (2 ' -pyridyl)-6-oxo-2H-tetrazine (dipyvdH) and triethylamine resulted in the neutral coordination compounds M(dipyvd)(2) (M = Ni,Zn). In acetonitrile, both compounds undergo two one electron oxidation processes, Zn (dipyvd)(2) at -0.28 V and -0.12 V and Ni(dipyvd)(2) at -0.32 V and -0.15 V vs ferrocene/ferricenium. Oxidations are ligand based resulting in an intermediate mixed valence species and a cationic bis(verdazyl) compound respectively. Oxidation of the ligand changes a localized, antiaromatic, non-planar 8 pi electron anion to a planar, delocalized 7 pi electron radical. The change in ligand structure results in an increase in the octahedral ligand field splitting from 10,500 cm(-1) to similar to 13,000 cm(-1), suggesting an increase in the pi acceptor character of the ligand. In the mixed valence species, spectroscopic data suggests minimal interaction between ligands mediated by the metal center; i.e., these are class I-II systems in the Robin-Day classification.

Automated summary

This study investigates the reaction of nickel and zinc triflates with a tridentate leucoverdazyl ligand, resulting in two neutral coordination compounds. Both compounds undergo ligand-based oxidations in acetonitrile, resulting in an intermediate mixed valence species and a cationic compound.