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

Huayi Fang; Huize Jing; Haonan Ge; Penelope J Brothers; Xuefeng Fu; Shengfa Ye

doi:10.1021/jacs.5b01121

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

J Am Chem Soc. 2015 Jun 10;137(22):7122-7. doi: 10.1021/jacs.5b01121. Epub 2015 Jun 2.

Authors

Huayi Fang¹, Huize Jing¹, Haonan Ge¹, Penelope J Brothers², Xuefeng Fu¹, Shengfa Ye³

Affiliations

¹ †Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
² ‡School of Chemical Sciences, University of Auckland, Private Bag 92019, Auckland 1042, New Zealand.
³ §Max-Planck Institute for Chemical Energy Conversion, Stiftstraße 34-36, D-45470 Mülheim an der Ruhr, Germany.

PMID: 25985282
DOI: 10.1021/jacs.5b01121

Abstract

(TPFC)Ge(TEMPO) (1, TPFC = tris(pentafluorophenyl)corrole, TEMPO(•) = (2,2,6,6-tetramethylpiperidin-1-yl)oxyl) shows high reactivity toward E-H (E = N, O) bond cleavage in R1R2NH (R1R2 = HH, (n)PrH, (i)Pr2, 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-H bond activation by [(TPFC)Ge](0)(2)/TEMPO(•) radical pair, generated by photocleavage of the labile Ge-O bond in compound 1, involving two sequential steps: (i) coordination of substrates to [(TPFC)Ge](0) and (ii) E-H bond cleavage induced by TEMPO(•) through proton coupled electron transfer (PCET).