Electronic structure and reactivity studies of a nonsymmetric one-electron oxidized CuII bis-phenoxide complex

Linus Chiang, Erik C. Wasinger, Yuichi Shimazaki, Victor Young, Tim Storr, T. Daniel P. Stack

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The tetradentate mixed imino/amino phenoxide ligand (N-(3,5-di-tert-butylsalicylidene)-N′-(2-hydroxyl-3,5-di-tert-butylbenzyl))-trans-1,2-cyclohexanediamine (salalen) was complexed with CuII, and the resulting Cu complex (2) was characterized by a number of experimental techniques and theoretical calculations. Two quasi-reversible redox processes for 2, as observed by cyclic voltammetry, demonstrated the potential stability of oxidized forms, and also the increased electron-donating ability of the salalen ligand in comparison to the salen analogue. The electronic structure of the one-electron oxidized [2]+ was studied in detail, and Cu K-edge X-ray Absorption Spectroscopy (XAS) measurements confirmed a CuII-phenoxyl radical complex in solution. Resonance Raman (rR) and variable temperature 1H NMR studies, coupled with theoretical calculations, showed that [2[rad]]+ is a triplet (S = 1) CuII-phenoxyl radical species, with localization of the radical on the more electron-rich aminophenoxide. Attempted isolation of X-ray quality crystals of [2[rad]]+ afforded [2H]+, with a protonated phenol bonded to CuII, and an additional H-bonding interaction with the SbF6 counterion. Stoichiometric reaction of dilute solutions of [2[rad]]+ with benzyl alcohol showed that the complex reacts in a similar manner as the oxidized CuII-salen analogue, and does not exhibit a substrate-binding pre-equilibrium as observed for the oxidized bis-aminophenoxide CuII-salan derivative.

Original languageEnglish (US)
Pages (from-to)151-158
Number of pages8
JournalInorganica Chimica Acta
StatePublished - Sep 1 2018

Bibliographical note

Funding Information:
This work was supported by a NIH grant (GM-120187) to TDPS, TS thanks NSERC for a postdoctoral scholarship. Westgrid is thanked for access to computational resources. We acknowledge Prof. Yoshinori Naruta and Prof. Fumito Tani of Kyushu University for measurement of the resonance Raman spectra, and this work was supported in part by the Cooperative Research Program of “Network Joint Research Center for Materials and Devices” (Institute for Materials Chemistry and Engineering, Kyushu University). ECW thanks CSU Chico College of Natural Sciences for start-up funding. Dr. Benjamin Kucera is acknowledged for assistance with X-ray crystallography. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. The SSRL Structural Molecular Biology Program is supported by the DOE Office of Biological and Environmental Research, and by the National Institutes of Health, National Institute of General Medical Sciences (including P41GM103393). The contents of this publication are solely the responsibility of the authors and do not necessarily represent the official views of NIGMS or NIH.

Publisher Copyright:
© 2017 Elsevier B.V.


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