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          Institute: MPI für bioanorganische Chemie     Collection: MPI für bioanorganische Chemie     Display Documents

ID: 683894.0, MPI für bioanorganische Chemie / MPI für bioanorganische Chemie
A Heterobimetallic Approach To Stabilize the Elusive Disulfur Radical Trianion ("Subsulfide") S2∙3-
Authors:Yao, Shenglai; Hrobárik, Peter; Meier, Florian; Rudolph, Robert; Bill, Eckhard; Irran, Elisabeth; Kaupp, Martin; Driess, Matthias
Date of Publication (YYYY-MM-DD):2013
Title of Journal:Chemistry A European Journal
Journal Abbrev.:Chem. Eur. J.
Start Page:1246
End Page:1253
Review Status:Peer-review
Audience:Experts Only
Abstract / Description:A unique heterobimetallic disulfur monoradical, complex 2, with a diamond-shaped {NiS2Pt} core has been synthesized by two-electron reduction of a supersulfido-(nacnac)nickel(II) complex (nacnac=&beta-diketiminato) with [Pt(Ph3P)(2)(&eta(2)-C2H4)] 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 (S-2(&Bull3-)) and two separated S2- 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.
Free Keywords:dichalcogens; nickel; oxidation states; platinum; redox ligands
External Publication Status:published
Document Type:Article
Communicated by:N. N.
Affiliations:MPI für bioanorganische Chemie
External Affiliations:Yao, S.; Rudolph, R.; Irran, E.; Driess, M.; Tech Univ Berlin, Dept Chem Met Organ & Inorgan Mat, D-10623 Berlin, Germany.
Hrobarik, P.; Meier, F.; Kaupp, M.;Tech Univ Berlin, Dept Chem Theoret Chem, D-10623 Berlin, Germany.
Identifiers:ISI:000313721500014 [ID No:1]
ISSN:0947-6539 [ID No:2]
DOI:10.1002/chem.201203642 [ID No:3]
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