Hayes EC1, Porter TR1, Barrows CJ1, Kaminsky W1, Mayer JM1, Stoll S1.
J Am Chem Soc. 2016 Mar 30;138(12):4132-45. doi: 10.1021/jacs.5b13088. Epub 2016 Mar 18.In the copper-catalyzed oxidation of alcohols to aldehydes, a Cu(II)-alkoxide (Cu(II)-OR) intermediate is believed to modulate the αC-H bond strength of the deprotonated substrate to facilitate the oxidation. As a structural model for these intermediates, we characterized the electronic structure of the stable compound Tp(tBu)Cu(II)(OCH2CF3) (Tp(tBu) = hydro-tris(3-tert-butyl-pyrazolyl)borate) and investigated the influence of the trifluoroethoxide ligand on the electronic structure of the complex. Read More