共 45 条
Formation of Highly Strained N-Heterocycles via Decomposition of Iron N-Heterocyclic Carbene Complexes: The Value of Labile Fe-C Bonds
被引:17
|作者:
Haslinger, Stefan
[1
]
Kueck, Jens W.
[1
]
Anneser, Markus R.
[1
]
Cokoja, Mirza
[2
]
Poethig, Alexander
[3
]
Kuehn, Fritz E.
[1
]
机构:
[1] Tech Univ Munich, Chair Inorgan Chem Mol Catalysis, D-85747 Garching, Germany
[2] Tech Univ Munich, Chair Inorgan & Organometall Chem, D-85747 Garching, Germany
[3] Tech Univ Munich, Catalysis Res Ctr, D-85747 Garching, Germany
关键词:
biimidazolium;
iron;
nitrogen heterocycles;
oxidation;
reductive elimination;
NONHEME IRON;
H BONDS;
OXIDATION;
EPOXIDATION;
ACTIVATION;
CATALYST;
H2O2;
DERIVATIVES;
REACTIVITY;
CHEMISTRY;
D O I:
10.1002/chem.201503282
中图分类号:
O6 [化学];
学科分类号:
0703 ;
摘要:
An unusual, highly-strained annulated 2,2'-biimdazole was isolated as decomposition product of the outer-sphere one-electron oxidation of an iron(II) N-heterocyclic carbene (NHC) complex bearing a tetradentate bis(NHC)-bis(pyridine) ligand (NCCN). Reductive elimination leading to the 2,2'-biimdazole is a consequence of the lability of the Fe-C bonds in the transient species and also extends to complexes with modified ligands but the same coordination geometry. Closely related by a two-electron redox step to a family of less-strained tetraazafulvalenes, the obtained 2,2'-biimidazolium salts were studied electrochemically. Introduction of methyl substituents at the methylene tether significantly increased the reversibility of the electrochemical reduction. Furthermore, the reactivity of the 2,2'-biimidazolium salt was examined by oxidative addition of [Ni(cod)(2)] to the central C-C bond, providing a previously unknown way for the formation of NHC transition metal complexes.
引用
收藏
页码:17860 / 17869
页数:10
相关论文