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.

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