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Título

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

AutorMartínez-Salvador, Sonia ; Alonso, Pablo J.; Forniés, Juan ; Martín, Antonio ; Menjón, Babil
Fecha de publicación2011
EditorRoyal Society of Chemistry (Great Britain)
CitaciónDalton Transactions 40(40): 10440-10447 (2011)
ResumenThe 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(CF 3)3Cl3] (5) by treatment with the stoichiometrically required amount of HCl(aq). Stereoisomer [NBu 4]2[mer-Pt(CF3)3Cl3] (6) has been obtained by oxidative addition of Cl2 to the organoplatinum(ii) precursor [NBu4]2[Pt(CF 3)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. © 2011 The Royal Society of Chemistry.
URIhttp://hdl.handle.net/10261/52651
DOI10.1039/C1DT10557D
Identificadoresdoi: 10.1039/C1DT10557D
issn: 1477-9226
e-issn: 1477-9234
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