title: A heterobimetallic approach to stabilize the elusive disulfur radical trianion ("subsulfide") S2(·3-).
abstract: A unique heterobimetallic disulfur monoradical, complex 2, with a diamond-shaped {NiS(2)Pt} core has been synthesized by two-electron reduction of a supersulfido-(nacnac)nickel(II) complex (nacnac=β-diketiminato) with [Pt(Ph(3)P)(2)(η(2)-C(2)H(4))] as a platinum(0) source and isolated in 82% yield. Strikingly, the results of DFT calculations in accordance with spectroscopic (EPR, paramagnetic NMR) and structural features of the complex revealed that the bonding situation of the S(2) ligand is between the elusive "half-bonded" S(2) radical trianion (S2(·3-)) and two separated S(2-) ligands and two separated S(2-) ligands. Accordingly, the Ni(II) center is partially oxidized, whereas the Pt(II) site is redox innocent. The complex can be reversibly oxidized to the corresponding Ni,Pt-disulfido monocation, compound 3, with a S--S single bond, and reacts readily with O(2) to form the corresponding superoxonickel(II) and disulfidoplatinum(II) (4) complexes. These compounds have been isolated in crystalline form and fully characterized, including IR and multi-nuclear NMR spectroscopy as well as ESI mass spectrometry. The molecular structures of compounds 2-4 have been confirmed by single-crystal X-ray crystallography.
authors.affiliation: Technische Universität Berlin, Department of Chemistry, Metalorganics and Inorganic Materials, Sekr. C2, Strasse des 17. Juni 135, 10623 Berlin, Germany.
authors.forename: Shenglai
authors.initials: S
authors.lastname: Yao
authors.forename: Peter
authors.initials: P
authors.lastname: Hrobárik
authors.forename: Florian
authors.initials: F
authors.lastname: Meier
authors.forename: Robert
authors.initials: R
authors.lastname: Rudolph
authors.forename: Eckhard
authors.initials: E
authors.lastname: Bill
authors.forename: Elisabeth
authors.initials: E
authors.lastname: Irran
authors.forename: Martin
authors.initials: M
authors.lastname: Kaupp
authors.forename: Matthias
authors.initials: M
authors.lastname: Driess