Title
Heteroleptic and Homoleptic Iron(III) Complexes with a Tris(N-Heterocyclic Carbene) Borate Ligand: Synthesis, Characterization, and Catalytic Application.
Author
Sato, Yuna, Masaya Okamura, and Shiro Hikichi
Year
2023
Journal
European Journal of Inorganic Chemistry
Abstract
Heteroleptic and homoleptic Iron(III) complexes supported by a tris(N-heterocyclic carbene) borate ligand have been prepared and crystallographically characterized. The strong electron-donating character of the tris(carbene) donor was revealed by UV-vis absorption spectroscopy and electrochemical measurements combined with quantum chemical calculations. The catalytic activity of each complex was evaluated in cyclohexane oxidation reaction using meta-chloroperoxybenzoic acid (= mCPBA) as an oxidant, and both complexes show high catalytic activity and selectivity with TON = ~350 and A/(K+L) = 8-10. Mechanistic studies suggested that radical-chain processes are involved in the reaction due to mCPBA acting as a one-electron oxidant, concomitant with the pathway of metal-based reactive species. Moreover, it was found that the homoleptic and heteroleptic complexes differed significantly in the involvement of metal-based active species, with the homoleptic complex exhibiting more metal-based reactions.
Instrument
V-730
Keywords
homogeneous catalysis