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Issue 3, 2014
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Germanium(iii) corrole complex: reactivity and mechanistic studies of visible-light promoted N–H bond activations

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Abstract

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(III) radical, [(TPFC)Ge(III)]˙. DFT calculations show that the spin density on the germanium center in [(TPFC)Ge(III)]˙ has a significant s character. Under visible-light irradiation, 1 reacts rapidly with ammonia, primary/secondary aliphatic amines and aniline to produce (TPFC)Ge–NR1R2 (R1R2 = HH, HnPr, HiPr, HtBu, HPh, Et2, iPr2) complexes in high yields (65–95%).

Graphical abstract: Germanium(iii) corrole complex: reactivity and mechanistic studies of visible-light promoted N–H bond activations

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Article information


Submitted
20 Aug 2013
Accepted
29 Oct 2013
First published
29 Oct 2013

Chem. Sci., 2014,5, 916-921
Article type
Edge Article

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

H. Fang, Z. Ling, K. Lang, P. J. Brothers, B. de Bruin and X. Fu, Chem. Sci., 2014, 5, 916
DOI: 10.1039/C3SC52326H

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