Noninnocent β-Diiminate Ligands: Redox Activity of a Bis(alkylimidazole)methane Ligand in Cobalt and Zinc Complexes

4 years ago

Noninnocent β-Diiminate Ligands: Redox Activity of a Bis(alkylimidazole)methane Ligand in Cobalt and Zinc Complexes

Robertus J. M. Klein Gebbink, Marc-Etienne Moret, Charl F. Riemersma, Martin Lutz, Richard Naastepad, Pradip Ghosh

A new β-diiminate ligand (the bis(1-methyl-4,5-diphenyl-1H-imidazol-2-yl)methane anion, BMIMPh2−) is introduced, in which the ligand framework bears an extended imidazole-based π-system in conjugation with a formal β-diketiminates (NacNac) backbone. Bis-ligated transition metal complexes (Co, Zn) featuring this anionic ligand undergo a series of four consecutive single-electron oxidations that are all ligand-based. The singly and doubly oxidized complexes can be synthesized on a preparative scale and have been fully characterized by various spectroscopic techniques. This is in sharp contrast to the corresponding NacNac-based complexes in which only singly oxidized complexes were isolated and characterized. Single crystal X-ray structure determination revealed a correlation between the intra-ligand metrical parameters and the oxidation state of BMIMPh2−. These structural changes in the ligand framework make BMIMPh2− as a perceptible non-innocent ligand in contrast to NacNac type ligands. Guilty as charged! Homoleptic transition metal complexes of a new class of β-diiminate ligand can undergo four ligand-based single-electron oxidations in total. The redox non-innocence of the ligand is perceptible by means of single crystal structural analysis.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201701215