Synthesis and Oxidation of a Paddlewheel‐Shaped Rhodium/Antimony Complex Featuring Pyridine‐2‐Thiolate Ligands. Issue 14 (9th February 2017) - Wächtler, Erik
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( κ 2 ‐pyS)]2 (2 ) is formed. Both1 and2 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 in1 and2 . Both covalent (Rh−Sb, X‐type Sb ligand) and dative (Rh→Sb, Z‐type; Rh←SbL ‐type Sb ligand) interactions have to be considered for the description of their bonding situations. Abstract : A pyridine‐2‐thiolate‐based Rh‐Sb complex with paddlewheel‐shaped architecture was synthesized from Rh I and Sb III starting materials. The reaction of this heterobimetallic complex with ONMe3 afforded the oxidation product. Both compounds feature Rh−Sb bonds and the ligand characteristics of Sb were analyzed by means of 121 Sb Mössbauer spectroscopy and DFT calculations.