Activation of CO2, CS2, and Dehydrogenation of Formic Acid Catalyzed by Iron(II) Hydride Complexes

被引：17

作者：

Wang, Lin ^{[1
]}

Sun, Hongjian ^{[1
]}

Zuo, Zhenyu ^{[1
]}

Li, Xiaoyan ^{[1
]}

Xu, Weiqin ^{[2
]}

Langer, Robert ^{[2
]}

Fuhr, Olaf ^{[3
]}

Fenske, Dieter ^{[3
]}

机构：

[1] Shandong Univ, Key Lab Special Funct Aggregated Mat, Sch Chem & Chem Engn, Minist Educ, Shanda Nanlu 27, Jinan 250199, Peoples R China

[2] Philipps Univ Marburg, Dept Chem, Hans Meerwein Str, D-35043 Marburg, Germany

[3] KIT, Inst Nanotechnol INT, Karlsruher Nanomicrofacil KNMF, Hermann von Helmholtz Pl 1, D-76344 Eggenstein Leopoldshafen, Germany

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2016年 / 33期

基金：

美国国家科学基金会;

关键词：

Iron; Hydrides; Carbon dioxide; Carbon disulfide; Dehydrogenation; SMALL-MOLECULE ACTIVATION; FRUSTRATED LEWIS PAIRS; CARBON-DISULFIDE CS2; IRIDIUM COMPLEXES; MILD CONDITIONS; GRAPHENE OXIDE; DIOXIDE; INSERTION; HYDROGENATION; BONDS;

D O I：

10.1002/ejic.201600642

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Fluoroarylimine-stabilized iron(II) hydrides were used for the activation of CO2. The resulting iron(II) formate complex 6, which was obtained by formal CO2 insertion into the Fe-H bond, turned out to be unstable in solution. CO was suitable for the formation of stable analogues of complex 6. From the three-component reaction of CO, CO2, and iron hydride, a series of stable carbonyl formate iron(II) complexes 7-9 were generated. Iron(II) formate complex 6 could also be obtained from the reaction of the iron(II) hydride complex with formic acid. On the basis of this result, the dehydrogenation of formic acid catalyzed by iron(II) hydrides was explored. The reaction was monitored by in situ H-1 NMR spectroscopy, and a possible mechanism was proposed. In addition, iron(II) hydrides also reacted with CS2 to generate thiocarboxy iron(II) complexes 12, 13, 14, and 16. Unexpected complex 17 was produced from the three-component reaction of CS2, complex 4, and compound 15. The possible mechanism of the three-component reaction was also studied by operando IR spectroscopy.

引用

页码：5205 / 5214

页数：10