Metal-chalcogen-nitrogen ring complexes and crystallographic studies

Abstract

A series of Pt(S₂N₂)(P(OR)[subscript n]R′[subscript(3-n)])₂ complexes were prepared and analysed using ³¹P NMR and IR spectroscopy, elemental analysis and X-ray crystallography. Similarly, a series of Pt(SeSN₂)(P(OR)[subscript n]R′[subscript(3-n)])₂ complexes were also prepared and analysed. The ¹J[subscript(Pt-P)] coupling constants and Pt-P bond lengths for these complexes are influenced by the oxygen content of their phosphorus ligands. The ³¹P NMR spectra for a series of [Pt(S3N)(P(OR)[subscript n]R′[subscript(3-n)])₂][BF₄] complexes are also reported. Planar [S₂N₂H]⁻ complexes were prepared and the X-ray crystal structure of [Pd(S₂N₂H)(bipy)][Cl] is reported.

The X-ray structures of MX₂(P(OR)[subscript n]R′[subscript(3-n)])₂ are reported and compared with the previously reported analogues. The magnitude of the ¹J[subscript(Pt-P)] varies linearly with the Pt-P bond length (l[subscript(Pt-P)] = 2.421 – J/24255) for the 12 platinum-containing complexes. This correlation is compared to that of a larger series of complexes.

A series of M(ndsdsd₂ (ndsdsd = bis[(nitrilo(diphenyl)-λ⁶-sulfanyl)](diphenyl)-λ⁶-sulfanediimide (Ph₂S(=N-(Ph₂)S≡N)₂)) complexes were prepared and characterised using elemental analysis and multinuclear NMR and IR spectroscopy where appropriate. The X-ray crystal structures of five examples are reported.