Reactions of olefin complexes with nitrene precursors. Synthesis of triazoline and aziridine complexes of palladium(II); crystal and molecular structure of trans-dichlorobis(11-phenyl-9,10,11-triazabicyclo-[6.3.0]undec-9-ene-N9)palladium-chloroform(1/2)

By reaction at 70 °C of phenyl azide with a suspension of PdCl2 and cis-cyclo-octene, the complex [PdCl2{N=N-N(Ph)-CH-CH-(CH2)5-CH 2}2]·2CHCl3 has been isolated, and its crystal and molecular structure determined. This compound crystallizes in triclinic space group P1 with a = 9.258(2), b = 10.702(3), c = 11.156(2) Å, α = 113.94(3), β = 99.60(2), γ = 104.87(3)°, and Z = 1. The metal lies on a symmetry centre and the complex configuration is trans planar. The chloroform molecules are hydrogen bonded to the co-ordinated chloride ions. The reaction of phenyl azide with cis-cyclo-octene at 70 °C in the absence of PdCl2 leads to the corresponding anil, N-cyclo-octylideneaniline, PhN=C-(CH2)6-CH2. Preformed [{PdCl2(cis-C8H14)}2] reacts with phenyl azide in cyclo-octene at 70 °C to give [PdCl2{N(Ph)-CH-CH-(CH2)5-CH2} 2]. By comparison, [{PdCl2[PhN=C-(CH2)6-CH2]} 2] has been synthesized from the reaction of [PdCl2(PhCN)2] with N-cyclo-octylideneaniline.