Dinitrogen complexes of osmium(II) with thiolate co-ligands: X-ray structure of mer-[OsCl(SC6F5)(N2)(PMe2Ph)3]

Abstract

Treatment of mer-[OsCl₂(N₂)(PMe₂Ph)₃] with S₂CNMe₂^– salts causes loss of N₂ and the formation of mer/fac-[OsCl(S₂CNMe₂)(PMe₂Ph)₃] and cis-[Os(S₂CNMe₂)₂(PMe₂Ph)₂]. Dinitrogen is, however, retained in reactions of mer-[OsX₂(N₂)(PMe₂Ph)₃](X = Cl or Br) with RS^–(R = Ph, C₆F₅, Me, or CF₃) at 20 °C in acetone to give the series mer-[OsX(SR)(N₂)(PMe₂Ph)₃]. Under more vigorous conditions the N₂ is displaced by thiolate. The compound mer-[OsCl(SC₆F₅)(N₂)(PMe₂Ph)₃] has an octahedral structure with N₂trans to chloride; d(N–N)= 1.112(5)Å and d(Os–S)= 2.507(1)Å.