Jump to main content
Jump to site search

Issue 40, 2011
Previous Article Next Article

Efficient and stereoselective syntheses of isomeric trifluoromethyl-platinum(IV) chlorides

Author affiliations


The homoleptic, square-planar trifluoromethylplatinate(II) compound [NBu4]2[Pt(CF3)4] (1) reacts with SOCl2 undergoing oxidative addition of a S–Cl bond to give the octahedral species [NBu4]2[trans-Pt(CF3)4Cl(SOCl)] (4), that contains the unusual chlorosulfinyl ligand. Compound 4 readily evolves into the dichloro-derivative [NBu4]2[cis-Pt(CF3)4Cl2] (2), whereby the “Pt(CF3)4” unit undergoes a stereochemical rearrangement from an initial square-planar (equatorial) geometry to a final sawhorse disposition within the global Pt octahedral environment. Compound 2 is more reactive than the corresponding [NBu4]2[trans-Pt(CF3)4Cl2] (3) stereoisomer and thus affords the trichloro-derivative [NBu4]2[fac-Pt(CF3)3Cl3] (5) by treatment with the stoichiometrically required amount of HCl(aq). Stereoisomer [NBu4]2[mer-Pt(CF3)3Cl3] (6) has been obtained by oxidative addition of Cl2 to the organoplatinum(II) precursor [NBu4]2[Pt(CF3)3Cl]. All the synthetic procedures described here proceed in high yields and in a stereoselective manner. The optical properties of the cis-/trans-[Pt(CF3)4Cl2]2 and fac-/mer-[Pt(CF3)3Cl3]2 diastereomeric couples (diffuse reflectance) as well as the solid-state geometries of the latter couple (single-crystal X-ray diffraction methods) are conveniently compared.

Graphical abstract: Efficient and stereoselective syntheses of isomeric trifluoromethyl-platinum(iv) chlorides

Back to tab navigation

Supplementary files

Publication details

The article was received on 01 Apr 2011, accepted on 25 May 2011 and first published on 15 Jul 2011

Article type: Paper
DOI: 10.1039/C1DT10557D
Citation: Dalton Trans., 2011,40, 10440-10447
  •   Request permissions

    Efficient and stereoselective syntheses of isomeric trifluoromethyl-platinum(IV) chlorides

    S. Martínez-Salvador, P. J. Alonso, J. Forniés, A. Martín and B. Menjón, Dalton Trans., 2011, 40, 10440
    DOI: 10.1039/C1DT10557D

Search articles by author