Synthesis and Oxidation of a Paddlewheel-Shaped Rhodium/Antimony Complex Featuring Pyridine-2-Thiolate Ligands

Erik Wächtler; Luis A Oro; Manuel Iglesias; Birgit Gerke; Rainer Pöttgen; Robert Gericke; Jörg Wagler

doi:10.1002/chem.201605485

Synthesis and Oxidation of a Paddlewheel-Shaped Rhodium/Antimony Complex Featuring Pyridine-2-Thiolate Ligands

Chemistry. 2017 Mar 8;23(14):3447-3454. doi: 10.1002/chem.201605485. Epub 2017 Feb 9.

Authors

Erik Wächtler^{1

2}, Luis A Oro², Manuel Iglesias², Birgit Gerke³, Rainer Pöttgen³, Robert Gericke¹, Jörg Wagler¹

Affiliations

¹ Institut für Anorganische Chemie, TU Bergakademie Freiberg, Leipziger Straße 29, 09596, Freiberg, Germany.
² Departamento Química Inorgánica-ISQCH, Universidad de Zaragoza-CSIC, C/Pedro Cerbuna 12, 50009, Zaragoza, Spain.
³ Institut für Anorganische und Analytische Chemie, WWU Münster, Corrensstraße 30, 48149, Münster, Germany.

PMID: 28083957
DOI: 10.1002/chem.201605485

Abstract

The paddlewheel-shaped complex [Sb(μ-pyS)₄ Rh]₂ (1) (pyS^- = 2-S-C₅ H₄ N^- ) was synthesized from [Rh(pyS)(cod)]₂ (cod=1,5-cyclooctadiene) and Sb(pyS)₃ . Upon oxidation with ONMe₃ , the complex [(μ-O)Sb(μ-pyS)₃ Rh(κ² -pyS)]₂ (2) is formed. Both 1 and 2 form dimers and feature short Rh-Sb bonds and bridging pyS ligands. ¹²¹ Sb Mössbauer spectro- scopy and computational studies were employed to elucidate the Rh-Sb bonding in 1 and 2. Both covalent (Rh-Sb, X-type Sb ligand) and dative (Rh→Sb, Z-type; Rh←Sb L-type Sb ligand) interactions have to be considered for the description of their bonding situations.

Keywords: antimony; coordination modes; heterobimetallic complexes; oxidation; rhodium.