A new P, S‐coordinating ferrocenyl ligand: synthesis of a precursor and its coordination compounds with PdII and PtII. Issue 5 (23rd April 2014)

• Record Type: Journal Article
• Authors: Mouas Toma, Nardjes; Daran, Jean‐Claude; Merazig, Hocine; Manoury, Eric
• Is Part Of: Acta crystallographica. Volume 70:Issue 5(2014:May)
• Page Start: 460
• Page End: 464
• Publication Date: 2014-04-23
• Subjects: Crystallography -- Periodicals; Crystals -- Periodicals; 548.3
• DOI: 10.1107/S2053229614007554
• Languages: English
• ISSNs: 2053-2296

Abstract

<abstract abstract-type="main" xml:lang="en"> <title> <x xml:space="preserve">Abstract</x> </title> <p>In our ongoing development of ferrocene ligands, 1‐dimethylamino‐2‐(diphenylphosphinothioyl)ferrocene is being used as a convenient building block to obtain racemic or enantiomerically pure ligands. Using this building block in large excess allowed the formation of several by‐products, two of which have already been reported; the structure of a third by‐product, namely 1‐(diphenylphosphinothioyl)‐2‐{[(diphenylphosphinothioyl)sulfanyl]methyl}ferrocene, [Fe(C<sub>5</sub>H<sub>5</sub>)(C<sub>30</sub>H<sub>25</sub>P<sub>2</sub>S<sub>3</sub>)], is presented here. The crystal structure is built up from a ferrocene unit, with one of the cyclopentadienyl (Cp) rings substituted in the 1‐ and 2‐positions by a protected diphenylphosphinothioyl group and a [(diphenylphosphinothioyl)sulfanyl]methyl fragment, –CH<sub>2</sub>SP(=S)Ph<sub>2</sub>. There are C—H...S interactions which result in the formation of chains parallel to the <italic>c</italic> axis. After desulfurization, the crude material was then reacted with Pd and Pt (<italic>M</italic>) precursors [<italic>M</italic>Cl<sub>2</sub>(CH<sub>3</sub>CN)<sub>2</sub>] to yield two isostructural dinuclear complexes arranged around twofold axes, namely (<italic>R</italic>, <italic>R</italic>/<italic>S</italic>, <italic>S</italic>)‐bis{μ‐[2‐(diphenylphosphanyl)ferrocen‐1‐yl]methanethiolato‐κ<sup>3</sup><italic>P</italic>, <italic>S</italic>:<italic>S</italic>}bis[chloridopalladium(II)] pentane disolvate, [Pd<sub>2</sub>{Fe(C<sub>5</sub>H<sub>5</sub>)(C<sub>18</sub>H<sub>15</sub>PS)}<sub>2</sub>Cl<sub>2</sub>]·2C<sub>5</sub>H<sub>12</sub>, and the platinum(II) analogue, (<italic>R</italic>, <italic>R</italic>/<italic>S</italic>, <italic>S</italic>)‐bis{μ‐[2‐(diphenylphosphanyl)ferrocen‐1‐yl]methanethiolato‐κ<sup>3</sup><italic>P</italic>, <italic>S</italic>:<italic>S</italic>}bis[chloridoplatinum(II)] toluene monosolvate, [Pt<sub>2</sub>{Fe(C<sub>5</sub>H<sub>5</sub>)(C<sub>18</sub>H<sub>15</sub>PS)}<sub>2</sub>Cl<sub>2</sub>]·C<sub>7</sub>H<sub>8</sub>, in which the two metal atoms present a slightly distorted square‐planar geometry formed by two bridging S atoms and P and Cl atoms. The <italic>P</italic>, <italic>S</italic>‐chelating ligand results from the rupture of one of the P—S bonds in the starting ligand. These dinuclear complexes display a butterfly geometry. Surprisingly, only the (<italic>R</italic>, <italic>R</italic>/<italic>S</italic>, <italic>S</italic>) diastereoisomer has been isolated.</p> </abstract>