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Article Dans Une Revue Acta Crystallographica Section C : Structural Chemistry [2014-...] Année : 2014

A new P,S-coordinating ferrocenyl ligand: synthesis of a precursor and its coordination compounds with PdII and PtII

Résumé

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]methylferrocene, [Fe(C5H5)(C30H25P2S3)], 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, -CH2SP(=S)Ph2. There are C-H...S interactions which result in the formation of chains parallel to the c axis. After desulfurization, the crude material was then reacted with Pd and Pt (M) precursors [MCl2(CH3CN)2] to yield two isostructural dinuclear complexes arranged around twofold axes, namely (R,R/S,S)-bis[mu]-[2-(diphenylphosphanyl)ferrocen-1-yl]methanethiolato-[kappa]3P,S:Sbis[chloridopalladium(II)] pentane disolvate, [Pd2Fe(C5H5)(C18H15PS)2Cl2].2C5H12, and the platinum(II) analogue, (R,R/S,S)-bis[mu]-[2-(diphenylphosphanyl)ferrocen-1-yl]methanethiolato-[kappa]3P,S:Sbis[chloridoplatinum(II)] toluene monosolvate, [Pt2Fe(C5H5)(C18H15PS)2Cl2].C7H8, 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 P,S-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 (R,R/S,S) diastereoisomer has been isolated.
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hal-02023141 , version 1 (18-02-2019)

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T. N. Mouas, Jean-Claude Daran, H. Merazig, E. Manoury. A new P,S-coordinating ferrocenyl ligand: synthesis of a precursor and its coordination compounds with PdII and PtII. Acta Crystallographica Section C : Structural Chemistry [2014-..], 2014, 70 (5), pp.460-464. ⟨10.1107/S2053229614007554⟩. ⟨hal-02023141⟩
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