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Acta Crystallogr Sect E Struct Rep Online. 2010 Mar 31;66(Pt 4):m477-8. doi: 10.1107/S1600536810011281.

Chloridotris(penta-fluoro-benzene-thiol-ato-κS)[tris-(4-fluoro-phen-yl)phosphine-κP]osmium(IV).

Abstract

The title complex, [Os(C(6)F(5)S)(3)Cl(C(18)H(12)F(3)P)], displays a trigonal-bipyramidal Os(IV) coordination geometry with the S atoms of three thiol-ate ligands occupying the equatorial positions. The thiol-ate penta-fluoro-phenyl substituents are all placed above the equatorial plane, forming a claw-like cavity which accommodates the chloride ligand with a normal Os-Cl bond length. The phosphine ligand trans to the chloride ligand reveals a short Os-P bond length compared to other chloride-phosphine Os(IV) complexes (average = 2.40 Å). This strong bonding indicates that the inductive effect of the F atoms in the phosphine does not affect significantly its basicity, compared to triphenyl-phosphine. This feature is also consistent with the known poor trans influence of Cl(-). The crystal packing involves π-π contacts between inversion-related thiol-ate C(6)F(5) rings, with a centroid-centroid separation of 3.659 (8) Å.

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