Effects of Charged Ligand Substituents on the Properties of the Formally Copper(III)-Hydroxide ([CuOH]2+) Unit

Debanjan Dhar, Gereon M. Yee, William B. Tolman

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16 Scopus citations

Abstract

With the goal of understanding how distal charge influences the properties and hydrogen atom transfer (HAT) reactivity of the [CuOH]2+ core proposed to be important in oxidation catalysis, the complexes [M]3[SO3LCuOH] (M = [K(18-crown-6)]+ or [K(crypt-222)]+) and [NMe3LCuOH]X (X = BArF 4 - or ClO4 -) were prepared, in which SO3 - or NMe3 + substituents occupy the para positions of the flanking aryl rings of the supporting bis(carboxamide)pyridine ligands. Structural and spectroscopic characterization showed that the [CuOH]+ cores in the corresponding complexes were similar, but cyclic voltammetry revealed the E1/2 value for the [CuOH]2+/[CuOH]+ couple to be nearly 0.3 V more oxidizing for the [NMe3LCuOH]2+ than the [SO3LCuOH]- species, with the latter influenced by interactions between the distal -SO3 - substituents and K+ or Na+ counterions. Chemical oxidations of the complexes generated the corresponding [CuOH]2+ species as evinced by UV-vis spectroscopy. The rates of HAT reactions of these species with 9,10-dihydroanthracene to yield the corresponding [Cu(OH2)]2+ complexes and anthracene were measured, and the thermodynamics of the processes were evaluated via determination of the bond dissociation enthalpies (BDEs) of the product O-H bonds. The HAT rate for [SO3LCuOH]- was found to be 150 times faster than that for [NMe3LCuOH]2+, despite finding approximately the same BDEs for the product O-H bonds. Rationales for these observations and new insights into the roles of supporting ligand attributes on the properties of the [CuOH]2+ unit are presented.

Original languageEnglish (US)
Pages (from-to)9794-9806
Number of pages13
JournalInorganic chemistry
Volume57
Issue number16
DOIs
StatePublished - Aug 20 2018

Bibliographical note

Funding Information:
We thank the National Institutes of Health (R37GM47365 to W.B.T.) and the Univ. of Minnesota (for the doctoral dissertation fellowship to D.D.) for financial support of this research, which was performed in the Dept. of Chemistry, Univ. of Minnesota. The authors thank Dr. V. G. Young, Jr., for assistance with X-ray crystallography. Some X-ray diffraction experiments were performed using a crystal diffractometer acquired through NSF-MRI Award No. CHE-1229400. We thank B. Dereli, Dr. M. Momeni, and Prof. C. J. Cramer for input and advice.

Publisher Copyright:
© Copyright 2018 American Chemical Society.

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