Multinuclear magnetic resonance study of Pt(II) compounds with sulfoxide ligands and crystal structures of complexes of the types [Pt(R2SO)X3]− and Pt(R2SO)2Cl2

Pt(II) complexes of the types K[Pt(R2SO)X3], NR4[Pt(R2SO)X3] and Pt(R2SO)2Cl2 (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)2Cl2 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)Cl3]−, 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 3J(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 2J(195Pt–13C) values vary between 35 and 66 Hz, while a few 3J(195Pt–13C) couplings were observed (13–26 Hz). The crystal structures of five monosubstituted ionic compounds N(n-Bu)4[Pt(TMSO)Cl3], N(Me)4[Pt(DPrSO)Cl3], K[Pt(EMSO)Cl3], K[Pt(TMSO)Br3] · H2O and N(Et)4[Pt(DPrSO)Br3] and one disubstituted complex cis-Pt(DBuSO)2Cl2 were determined. The trans influence of the different ligands is discussed.