Organometallics
Communication
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̈
nickel(III) state was critical for N−N bond formation from
binuclear nickel complexes.4 Electrochemical data support the
first oxidation as being irreversible, which is also consistent with
the rapid formation of product 8 from 10/11.
Various conditions for such N−N bond forming reactions
through cyclizations of an amino group with an imine (or
oxime) partner have been known since the early work of
Hassner and Michelson in the 1960s.22 However, to our knowl-
edge, this work represents the first characterization of a metal-
bound intermediate in such a reaction. The oxidation of 7 to 10
involves to a large degree ligand-centered redox chemistry, and
we hope that such knowledge will be useful in developing more
sophisticated reactions involving N−N bond formations.
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the ACS
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S
(17) Giffin, K. A.; Korobkov, I.; Baker, R. T. Dalton Trans. 2015, 44,
19587−19596.
(18) Lee, G. M.; Korobkov, I.; Baker, R. T. J. Organomet. Chem. 2017,
847, 270−277.
Cartesian coordinates of the calculuated structures
Experimental procedures, characterization data, NMR
(19) Harrison, D. J.; Daniels, A. L.; Korobkov, I.; Baker, R. T.
Organometallics 2015, 34, 5683−5686.
(20) Giffin, K. A.; Harrison, D. J.; Korobkov, I.; Baker, R. T.
Organometallics 2013, 32, 7424−7430.
spectra, and X-ray and computational data (PDF)
(21) Mitin, A. V.; Baker, J.; Pulay, P. J. Chem. Phys. 2003, 118, 7775−
7782.
Accession Codes
mentary crystallographic data for this paper. These data can be
The Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
(22) Hassner, A.; Michelson, M. J. J. Org. Chem. 1962, 27, 298−301.
AUTHOR INFORMATION
Corresponding Author
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ORCID
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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D.A.V. thanks the Office of Basic Energy Sciences of the U.S.
Department of Energy (DE-SC0009363) for support of this
work. A.K. and A.S. are grateful for support by Deutsche
Forschungsgemeinschaft DFG KL1194/15-1, N.V. acknowl-
edges the PROMI program of the University of Cologne.
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