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

(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, 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–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).