3 years ago

Valence Interconversion of Octahedral Nickel(II/III/IV) Centers

Valence Interconversion of Octahedral Nickel(II/III/IV) Centers
Takumi Konno, Naoto Kuwamura, Nobuto Yoshinari, Akira Sekiyama, Kohei Yamagami, Mitsutaka Okumura, Masahiro Kouno
Three oxidation states (+2, +3, +4) of an octahedral nickel center were stabilized in a newly prepared RhNiRh trinuclear complex, [Ni{Rh(apt)3}2]n+ (apt=3- aminopropanethiolate), in which the nickel center was bound by six thiolato donors sourced from two redox-inert fac-[RhIII(apt)3] octahedral units. The three oxidation states of the octahedral nickel center were fully characterized by single-crystal X-ray crystallography, as well as spectroscopic, electrochemical, and magnetic measurements; all three were interconvertible, and the conversion was accompanied by changes in color, magnetism, and Jahn–Teller distortion. Bridge over troubled water: A series of S-bridged RhNiRh trinuclear complexes capable of supporting an octahedral nickel center in three different oxidation states (+2, +3, +4) have been isolated. Oxidation state interconversion is accompanied by changes in color, magnetism, and geometric Jahn–Teller distortions, with retention of the trinuclear structure.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201708169

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