31P CP-MAS NMR,Vibrational, and X-Ray Characterization of the Adducts of Triphenylphosphine Sulfide with ICl and IBr

The reactions between triphenylphosphine sulfide (Ph₃PS) and ICl in CCl₄ and IBr in CH₂Cl₂ in 1 : 1 molar ratio give the solid adducts Ph₃PS · ICl ( I ) and Ph₃PS · IBr ( II ) whose structures have been solved by X-ray diffraction. Compounds I and II consist of discrete molecule units and feature the S–I–Cl or S–I–Br linear group. The S–I bond distances in I , II (2.641(1), 2.665(1) Å respectively) and in compound 2 Ph₃PS · 3 I₂ ( III ) (2.729(2) Å) are correlable to the net increase in the I–X (X = Cl, Br, I) bond distance. The structural features of I , II and III are in accordance with ³¹P CP–MAS NMR, FT-Raman and FT-IR spectral data, and elucidate the nature of the donor (Ph₃PS)-acceptor (ICl, IBr, I₂) interaction.