Germanium(III) corrole complex: reactivity and mechanistic studies of visible-light promoted N-H bond activations

被引：43

作者：

Fang, Huayi ^{[1
]}

Ling, Zhen ^{[1
]}

Lang, Ke ^{[1
]}

Brothers, Penelope J. ^{[2
]}

de Bruin, Bas ^{[3
]}

Fu, Xuefeng ^{[1
]}

机构：

[1] Peking Univ, Coll Chem & Mol Engn, Beijing Natl Lab Mol Sci, Beijing 100871, Peoples R China

[2] Univ Auckland, Sch Chem Sci, Auckland 1042, New Zealand

[3] Univ Amsterdam, Vant Hoff Inst Mol Sci HIMS, NL-1098 XH Amsterdam, Netherlands

来源：

CHEMICAL SCIENCE | 2014年 / 5卷 / 03期

关键词：

AMIDO HYDRIDE COMPLEX; MAIN-GROUP ELEMENTS; ELECTRONIC-STRUCTURE; OXIDATIVE ADDITION; AMMONIA; RADICALS; CLEAVAGE; GE; ELIMINATION; NITROXIDES;

D O I：

10.1039/c3sc52326h

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The [(TPFC)Ge(TEMPO)] (1, TPFC = tris(pentafluorophenyl)corrole, TEMPO = (2,2,6,6-tetramethylpiperidin-1-yl)oxyl) complex was characterized by X-ray diffraction and spectroscopic studies. EPR studies indicate that the weak Ge-O bond in 1 is photo-cleaved to form a tetra-coordinated germanium(m) radical, [(TPFC)Ge(III)](center dot). DFT calculations show that the spin density on the germanium center in [(TPFC)Ge(III)](center dot). has a significant s character. Under visible-light irradiation, 1 reacts rapidly with ammonia, primary/secondary aliphatic amines and aniline to produce (TPFC)Ge-(NRR2)-R-1 ((RR2)-R-1 = HH, (HPr)-Pr-n, (HPr)-Pr-i, (HBu)-Bu-t, HPh, Et-2, Pr-i(2)) complexes in high yields (65-95%).

引用

页码：916 / 921

页数：6

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