Heteroleptic and Homoleptic Iron(III) Complexes with a Tris(N-Heterocyclic Carbene) Borate Ligand: Synthesis, Characterization, and Catalytic Application

被引:4
作者
Sato, Yuna [1 ]
Okamura, Masaya [1 ]
Hikichi, Shiro [1 ]
机构
[1] Kanagawa Univ, Fac Engn, Dept Mat & Life Chem, 3-27-1 Rokkakubashi, Yokohama, Kanagawa 2218686, Japan
关键词
alkanes; carbene ligands; homogeneous catalysis; iron; oxidation; NONHEME IRON COMPLEX; ELECTROCHEMICAL PROPERTIES; OXIDATION; REACTIVITY; APPROXIMATION; HYDROXYLATION; MECHANISM;
D O I
10.1002/ejic.202200728
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
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=similar to 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.
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页数:9
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