A Heterobimetallic Approach To Stabilize the Elusive Disulfur Radical Trianion ("Subsulfide") ${{\rm S}{{{{\bullet}}3- \hfill \atop 2\hfill}}}$. Issue 4 (18th December 2012)

• Record Type: Journal Article
• Authors: Yao, Shenglai; Hrobárik, Peter; Meier, Florian; Rudolph, Robert; Bill, Eckhard; Irran, Elisabeth; Kaupp, Martin; Driess, Matthias
• Is Part Of: Chemistry. Volume 19:Issue 4(2013)
• Page Start: 1246
• Page End: 1253
• Publication Date: 2012-12-18
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201203642
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>A unique heterobimetallic disulfur monoradical, complex <bold>2</bold>, with a diamond‐shaped {NiS<sub>2</sub>Pt} core has been synthesized by two‐electron reduction of a supersulfido‐(nacnac)nickel(II) complex (nacnac=β‐diketiminato) with [Pt(Ph<sub>3</sub>P)<sub>2</sub>(η<sup>2</sup>‐C<sub>2</sub>H<sub>4</sub>)] 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<sub>2</sub> ligand is between the elusive "half‐bonded" S<sub>2</sub> radical trianion (<tex-math notation="tex"><![CDATA[${{\rm S}{{{{\bullet}}3- \hfill \atop 2\hfill}}}$]]></tex-math><inline-graphic xlink:href="ark:/27927/pgg1p9fv1hb" mimetype="image" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" />) and two separated S<sup>2−</sup> ligands. Accordingly, the Ni<sup>II</sup> center is partially oxidized, whereas the Pt<sup>II</sup> site is redox innocent. The complex can be reversibly oxidized to the corresponding Ni, Pt‐disulfido monocation, compound <bold>3</bold>, with a SS single bond, and reacts readily with O<sub>2</sub> to form the corresponding superoxonickel(II) and disulfidoplatinum(II) (<bold>4</bold>) 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 <bold>2</bold>–<bold>4</bold> have been confirmed by single‐crystal X‐ray crystallography.</p> </abstract>