POLYSULFONYLAMINE: TEIL XXVIII.¹ REAKTION VON N-CHLORDIMESYLAMIN MIT EINIGEN PHOSPHOR(III)-VERBINDUNGEN. RÖNTGENSTRUKTURANALYSEN VON [ⁱPr₃PCl] ⁺⁻N(SO₂Me)₂. CH₂Cl₂ UND (PhO)₃P[dbnd]NSO₂Me

Abstract

N-Chloro-dimesylamine ClN(SO₂Me)₂ (1) reacts with the appropriate triorganophosphines to give the ionic chloro(triorgano)phosphonium dimesylamides R₃PCI^{+ −}N(SO₂Me)₂ [R = ⁱPr (2a), ⁿBu (2b), Ph (2c)]. The reaction of 1 with (MeO)₃P affords (MeO)₂P(O)Cl and MeN(SO₂Me)₂; its reaction with (PhO)₃P or PCl₃ leads to elimination of MeSO₂Cl and formation of the phosphine imides Y₃P[dbnd]NSO₂Me [Y = PhO (3a), Cl (3b)]. The (1/1) dichloromethane solvate of 2a crystallizes in the monoclinic space group P2₁/c with a = 1735.6(7), b = 841.1(4), c = 1658.4(7) pm, β = 118.34(3)°, U = 2.1309(16) nm³, Z = 4. The crystal lattice consists of discrete ⁱPr₃PCl⁺ cations (P[sbnd]Cl 199.4 pm, bond angles at P 105.7–117.5°), (MeSO₂)₂N⁻ anions and CH₂Cl₂ molecules apparently hydrogen-bonded to oxygen atoms of the anions. 3a crystallizes in the monoclinic space group P2₁/c with a = 974.7(3), b = 2052.3(6), c = 959.5(3) pm, β = 98.820(14)°, U = 1.8967(10) nm³, Z = 4. The dimensions of the molecule (P[sbnd]N 154.4, N[sbnd]S 159.8 pm, P[sbnd]N[sbnd]S 126.2°) are consistent with a delocalized electronic structure in the P[sbnd]N[sbnd]S system.

Key Words:

• N-Chloro-dimesylamine
• Triorganophosphines
• Triorganophosphites
• Phosphorus trichloride
• chloro(triorgano)phosphonium dimesylamides
• N-mesyl phosphine imides
• X-ray structures.