Valence Interconversion of Octahedral Nickel(II/III/IV) Centers. Issue 44 (22nd September 2017)

• Record Type: Journal Article
• Authors: Kouno, Masahiro; Yoshinari, Nobuto; Kuwamura, Naoto; Yamagami, Kohei; Sekiyama, Akira; Okumura, Mitsutaka; Konno, Takumi
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 44(2017)
• Page Start: 13762
• Page End: 13766
• Publication Date: 2017-09-22
• Subjects: high oxidation states -- nickel -- redox chemistry -- sulfur ligands; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201708169
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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 ‐[Rh III (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. Abstract : 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.