Abstract
Pt(II) complexes of the types K[Pt(R 2SO)X 3], NR 4[Pt(R 2SO)X 3] and Pt(R 2SO) 2Cl 2 (where X = Cl or Br) were characterized by multinuclear magnetic resonance spectroscopy ( 195Pt, 1H and 13C). In 195Pt NMR, the chloro ionic compounds have shown signals between −2979 and −3106 ppm, while the cis disubstituted complexes were observed at higher fields, between −3450 and −3546 ppm. The signal of the compound trans-Pt(DPrSO) 2Cl 2 was found at higher field (−3666 ppm) than its cis analogue (−3517 ppm), since π-back-donation is considerably less effective in the trans geometry. In 1H NMR, a single signal was observed for the sulfoxide in [Pt(DMSO)Cl 3] −, but for the other more sterically hindered ligands, two series of resonances were observed for the protons in α and β positions. The coupling constant 3 J( 195Pt– 1H) are between 15 and 33 Hz. The 13C NMR results were interpreted in relation to the concept of inversed polarization of the π sulfoxide bond. The 2 J( 195Pt– 13C) values vary between 35 and 66 Hz, while a few 3 J( 195Pt– 13C) couplings were observed (13–26 Hz). The crystal structures of five monosubstituted ionic compounds N( n-Bu) 4[Pt(TMSO)Cl 3], N(Me) 4[Pt(DPrSO)Cl 3], K[Pt(EMSO)Cl 3], K[Pt(TMSO)Br 3] · H 2O and N(Et) 4[Pt(DPrSO)Br 3] and one disubstituted complex cis-Pt(DBuSO) 2Cl 2 were determined. The trans influence of the different ligands is discussed.
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