A new nitrogen heterocyclic carbene containing diiron complex as bio-inspired catalyst for proton reduction and benzen

作者：Wang, Yanhong; Yang, Yiwen; Zhang, Tianyong^*; Zhang, Xia; Jiang, Shuang; Zhang, Guanghui; Li, Bin^*

来源：Journal of Organometallic Chemistry, 2016, 825: 55-62.

DOI：10.1016/j.jorganchem.2016.10.020

• [Fe-Fe]-H(2)ases
• Nitrogen heterocyclic carbene
• Electrochemical property
• Proton reduction
• Catalytic hydroxylation

A new diiron complex (mu-dmedt)[Fe-2(Co)(5)IPr] (2, dmedt = 2,3-butanedithiol, IPr = 1,3-bis(2,6-diisopropylphenyl) imidazol-2-ylidene) was synthesized as analogue of the active site of [Fe-Fe]H(2)ases. The sterically bulky nitrogen heterocyclic carbene ligand of IPr coordinated to the iron center was introduced via CO/L substitution reaction in mild conditions. The reactivity of electrocatalytic reduction of proton and catalytic hydroxylation of benzene were explored for the developed diiron complex. Complex 2 undergoes two irreversible reduction events at ca. -2.17 V and -2.50 V and acts as an efficient electrocatalyst for proton reduction to hydrogen with both HOAc and H2O as proton source. The catalytic hydroxylation of benzene by complex 2 achieved phenol yield of 32.4% with almost 100% selectivity. The enhanced catalytic activity compared to the all carbonyl precursor and related derivatives was attributed to the good electron donating ability of introduced IPr ligand.

• 出版日期2016-12-15
• 单位天津大学; 中国石油化工股份有限公司上海石油化工研究院