Email RIS file
Bookmark
Report an Issue

Characterization and Reactivity of a Terminal Nickel(III)-Oxygen Adduct [electronic resource].

Published
Washington, D.C. : United States. Dept. of Energy. Office of Basic Energy Sciences, 2015.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy
Physical Description
pages 3,785-3,790 : digital, PDF file
Additional Creators
Brookhaven National Laboratory, United States. Department of Energy. Office of Basic Energy Sciences, and United States. Department of Energy. Office of Scientific and Technical Information
Access Online

Availability

I Want It
I Want It

Finding items...

Restrictions on Access
Free-to-read Unrestricted online access
Summary
Here, high-valent terminal metal–oxygen adducts are hypothesized to be the potent oxidizing reactants in late transition metal oxidation catalysis. In particular, examples of high-valent terminal nickel–oxygen adducts are scarce, meaning there is a dearth in the understanding of such oxidants. A monoanionic NiII-bicarbonate complex has been found to react in a 1:1 ratio with the one-electron oxidant tris(4-bromophenyl)ammoniumyl hexachloroantimonate, yielding a thermally unstable intermediate in high yield (ca. 95%). Electronic absorption, electronic paramagnetic resonance, and X-ray absorption spectroscopies and density functional theory calculations confirm its description as a low-spin (S=1/2), square planar NiIII–oxygen adduct. Moreover, this rare example of a high-valent terminal nickel–oxygen complex performs oxidations of organic substrates, including 2,6-di-tert-butylphenol and triphenylphosphine, which are indicative of hydrogen atom abstraction and oxygen atom transfer reactivity, respectively.
Report Numbers
E 1.99:bnl--111023-2015-ja
bnl--111023-2015-ja
Subject(s)
Note
Published through SciTech Connect.
01/22/2015.
"bnl--111023-2015-ja"
Chemistry - A European Journal 21 9 ISSN 0947-6539 AM
Paolo Pirovano; Erik R. Farquhar; Marcel Swart; Anthony J. Fitzpatrick; Grace G. Morgan; Aidan R. McDonald.
Funding Information
AC02–98CH10886
SC00112704
P30-EB-009998
UNGI08–4E-003
2014SGR1202
CTQ2011–25086/BQU
CM1305
SFI/12/RC/2278
View MARC record | catkey: 24045314