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Keywords:

  • Osmium;
  • Phosphoraneimine derivatives;
  • Crystal structures

Abstract

Phosphoraneimine Derivatives of Osmium(IV): Crystal Structures of trans-[OsCl4(HNPEt3)2] and (H2NPPh3)2[OsCl6]·2CH3CN

trans-[OsCl4(HNPEt3)2] (1) was prepared by reaction of osmium pentachloride with the silylated phosphoraneimine Me3SiNPEt3 in dichloromethane solution forming yellow moisture sensitive single crystals. The hexachloroosmate(IV) (H2NPPh3)2[OsCl6]·2CH3CN (2) was obtained as yellow single crystals from osmium pentachloride and N-chlorotriphenylphosphoraneimine, ClNPPh3, in acetonitrile solution. 1 and 2 are characterized by IR spectroscopy and single crystal X-ray structure determinations.

1: Space group P21/c, Z = 2, lattice dimensions at 193 K: a = 830.9(1), b = 1031.1(1), c = 1307.7(1) pm, β = 106.15(1)°, R1 = 0.0248. 1 forms centrosymmetric molecules with distances Os–N of 202.9(4) pm and Os–Cl of 234.7 pm on average.

2: Space group equation image, Z = 2, lattice dimensions at 193 K: a = 1030.7(1), b = 1432.6(1), c = 1448.8(1) pm, α = 90.98(1)°, β = 92.40(1)°, γ = 92.98(1)°, R1= 0.0545. 2 forms an ionic structure with (H2NPPh3)+ cations and two different site positions of the centrosymmetric [OsCl6]2− anions. The cations are connected with one of the anions by N-H···Cl bridges as well as with the solvate molecules CH3CN by N–H···N bridges.