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Highly trifluoromethylated platinum compounds

AuthorsMartínez-Salvador, Sonia ; Forniés, Juan ; Martín, Antonio ; Menjón, Babil
Issue Date2011
CitationChemistry - A European Journal 17(29): 8085-8097 (2011)
AbstractThe homoleptic, square-planar organoplatinum(II) compound [NBu 4]2[Pt(CF3)4] (1) undergoes oxidative addition of CF3I under mild conditions to give rise to the octahedral organoplatinum(IV) complex [NBu4]2[Pt(CF 3)5I] (2). This highly trifluoromethylated species reacts with Ag+ salts of weakly coordinating anions in Me2CO under a wet-air stream to afford the aquo derivative [NBu4] [Pt(CF3)5(OH2)] (4) in around 75% yield. When the reaction of 2 with the same Ag+ salts is carried out in MeCN, the solvento compound [NBu4][Pt(CF3)5(NCMe)] (5) is obtained in around 80% yield. The aquo ligand in 4 as well as the MeCN ligand in 5 are labile and can be cleanly replaced by neutral and anionic ligands to furnish a series of pentakis(trifluoromethyl)platinate(IV) compounds with formulae [NBu4][Pt(CF3)5(L)] (L=CO (6), pyridine (py; 7), tetrahydrothiophene (tht; 8)) and [NBu4] 2[Pt(CF3)5X] (X=Cl (9), Br (10)). The unusual carbonyl-platinum(IV) derivative [NBu4][Pt(CF3) 5(CO)] (6) is thermally stable and has a νCO of 2194 cm-1. The crystal structures of 2̇CH2Cl2, 5, [PPh4][Pt(CF3)5(CO)] (6'), and 7 have been established by X-ray diffraction methods. Compound 2 has shown itself to be a convenient entry to the chemistry of highly trifluoromethylated platinum compounds. To the best of our knowledge, compounds 2 and 4-10 are the organoelement compounds with the highest CF3 content to have been isolated and adequately characterized to date.
Identifiersdoi: 10.1002/chem.201100626
issn: 0947-6539
e-issn: 1521-3765
Appears in Collections:(ISQCH) Artículos
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