The Mechanism of E鈥揌 (E = N, O) Bond Activation by a Germanium Corrole Complex: A Combined Experimental and Computational Study

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• 作者：Huayi Fang ; Huize Jing ; Haonan Ge ; Penelope J. Brothers ; Xuefeng Fu ; Shengfa Ye
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：June 10, 2015
• 年：2015
• 卷：137
• 期：22
• 页码：7122-7127
• 全文大小：373K
• ISSN：1520-5126

文摘

(TPFC)Ge(TEMPO) (1, TPFC = tris(pentafluorophenyl)corrole, TEMPO^{鈥?/sup> = (2,2,6,6-tetramethylpiperidin-1-yl)oxyl) shows high reactivity toward E鈥揌 (E = N, O) bond cleavage in R₁R₂NH (R₁R₂ = HH, nPrH, iPr₂, Et₂, PhH) and ROH (R = H, CH₃) under visible light irradiation. Electron paramagnetic resonance (EPR) analyses together with the density functional theory (DFT) calculations reveal the E鈥揌 bond activation by [(TPFC)Ge]0(2)/TEMPO鈥?/sup> radical pair, generated by photocleavage of the labile Ge鈥揙 bond in compound 1, involving two sequential steps: (i) coordination of substrates to [(TPFC)Ge]0 and (ii) E鈥揌 bond cleavage induced by TEMPO鈥?/sup> through proton coupled electron transfer (PCET).}