AI Article Synopsis
- The compound TPFCGe(TEMPO) exhibits strong reactivity in breaking E-H bonds (where E can be nitrogen or oxygen) in various amines and alcohols when exposed to visible light.
- EPR analysis and DFT calculations show that the mechanism involves the formation of a radical pair from the photocleavage of a Ge-O bond in TPFCGe, leading to two main steps: substrate coordination and E-H bond cleavage.
- The bond cleavage process is mediated by TEMPO(•), utilizing a mechanism called proton coupled electron transfer (PCET) to activate the bond.
Article 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).
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| http://dx.doi.org/10.1021/jacs.5b01121 | DOI Listing |
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