Synthesis of silyl iron dinitrogen complexes for activation of dihydrogen and catalytic silylation of dinitrogen

被引：9

作者：

Chang, Guoliang ^{[1
]}

Zhang, Peng ^{[1
]}

Yang, Wenjing ^{[1
]}

Dong, Yanhong ^{[1
]}

Xie, Shangqing ^{[1
]}

Sun, Hongjian ^{[1
]}

Li, Xiaoyan ^{[1
]}

Fuhr, Olaf ^{[2
,3
]}

Fenske, Dieter ^{[2
,3
]}

机构：

[1] Shandong Univ, Sch Chem & Chem Engn, Key Lab Special Funct Aggregated Mat, Minist Educ, Shanda Nanlu 27, Jinan 250100, Peoples R China

[2] Karlsruher Inst Technol KIT, Inst Nanotechnol INT, Hermann von Helmholtz Pl 1, D-76344 Eggenstein Leopoldshafen, Germany

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

来源：

DALTON TRANSACTIONS | 2021年 / 50卷 / 47期

关键词：

H ACTIVATION; BEARING; REACTIVITY; N-2; REDUCTION; LIGANDS; COBALT; HYDROGENATION; CONVERSION; NITROGEN;

D O I：

10.1039/d1dt02832d

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Three novel iron dinitrogen hydrides, [FeH(Pr-i-(PSiP)-P-Me)(N-2)(PMe3)] (1), [FeH(Pr-i-(PSiP)-P-Ph)(N-2)(PMe3)] (2), and [FeH(Pr-i-PSiPh)(N-2)(PMe3)] (3), supported by a silyl ligand are synthesized for the first time by changing the electronic effect and steric hindrance of the ligands through the reaction of ligands L1-L3 with Fe(PMe3)(4) in a nitrogen atmosphere. The ligands containing an electron-donating group with large steric hindrance on the phosphorus atom are beneficial for the formation of dinitrogen complexes. A penta-coordinate iron hydride [FeH(Pr-i-PSiPh)(PMe3)(2)] (4) was formed through the reaction of ligand L3 with Fe(PMe3)(4) in an argon atmosphere under the same conditions. The reactions between complexes 1-3 with an atmospheric pressure of dihydrogen gas resulted in Fe(II) dihydrides, [(Pr-i-PSiMe(mu-H)P)Fe(H)(2)(PMe3)] (5), [(Pr-i-PSiPh(mu-H)P)Fe(H)(2)(PMe3)] (6) and [(iPr-PSiPh(mu-H))Fe(H)(2)(PMe3)(2)] (7), with an eta(2)-(Si-H) coordination. The isolation of dihydrides 5-7 demonstrates the ability of the dinitrogen complexes 1-3 to realize the activation of dihydrogen under ambient temperature and pressure. The molecular structures of complexes 1-7 were elucidated by single crystal X-ray diffraction analysis. The iron dinitrogen hydrides 1-3 are effective catalysts for the silylation of dinitrogen under ambient conditions and among them 3 is the best catalyst.

引用

页码：17594 / 17602

页数：9