title: Efficient and stereoselective syntheses of isomeric trifluoromethyl-platinum(IV) chlorides.
abstract: The homoleptic, square-planar trifluoromethylplatinate(II) compound [NBu(4)](2)[Pt(CF(3))(4)] (1) reacts with SOCl(2) undergoing oxidative addition of a S-Cl bond to give the octahedral species [NBu(4)](2)[trans-Pt(CF(3))(4)Cl(SOCl)] (4), that contains the unusual chlorosulfinyl ligand. Compound 4 readily evolves into the dichloro-derivative [NBu(4)](2)[cis-Pt(CF(3))(4)Cl(2)] (2), whereby the "Pt(CF(3))(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 [NBu(4)](2)[trans-Pt(CF(3))(4)Cl(2)] (3) stereoisomer and thus affords the trichloro-derivative [NBu(4)](2)[fac-Pt(CF(3))(3)Cl(3)] (5) by treatment with the stoichiometrically required amount of HCl(aq). Stereoisomer [NBu(4)](2)[mer-Pt(CF(3))(3)Cl(3)] (6) has been obtained by oxidative addition of Cl(2) to the organoplatinum(II) precursor [NBu(4)](2)[Pt(CF(3))(3)Cl]. All the synthetic procedures described here proceed in high yields and in a stereoselective manner. The optical properties of the cis-/trans-[Pt(CF(3))(4)Cl(2)](2-) and fac-/mer-[Pt(CF(3))(3)Cl(3)](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.
authors.affiliation: Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Facultad de Ciencias, Universidad de Zaragoza-C.S.I.C., C/Pedro Cerbuna 12, E-50009, Zaragoza, Spain.
authors.forename: Sonia
authors.initials: S
authors.lastname: Martínez-Salvador
authors.forename: Pablo J
authors.initials: PJ
authors.lastname: Alonso
authors.forename: Juan
authors.initials: J
authors.lastname: Forniés
authors.forename: Antonio
authors.initials: A
authors.lastname: Martín
authors.forename: Babil
authors.initials: B
authors.lastname: Menjón