Azidokomplexe von Vanadium(IV) und Vanadium(V): (Ph4P)2[VOCl2(μ‐N3)]2 und (Ph4P)2[VOCl(μ‐N3)(N3)2]2

Abstract

AbstractAzido Complexes of Vanadium(IV) and Vanadium(V): (Ph4P)2[VOCl2(μ‐N3)]2 and (Ph4P)2[VOCl(μ‐N3)(N3)2]2(Ph4P)2[VOCl2(μ‐N3)]2 (1) was prepared by reaction of (Ph4P)[VO2Cl2] with trimethylsilylazide in the molar ratio 1:2 in dichloromethane solution to give dark green, moisture sensitive, non‐explosive single crystals. The reaction is accompanied by the formation of the dark blue side‐product (Ph4P)2[VOCl(μ‐N3)(N3)2]2 (2a), which can be obtained as the main product by application of a large excess of Me3SiN3. Dark blue needles of 2a crystallize spontaneously from the CH2Cl2 solution within one hour at 4 °C. After standing at 4 °C under its mother liquid within 24 hours a first‐order phase transition of 2a occurs forming dark blue prismatic single crystals of 2b. According to single crystal X‐ray structure determinations, 2a and 2b crystallize in the same type of space group $\rm P{\bar 1}$, however, with different lattice dimensions.The vanadium(IV) complex 1 is characterized by X‐ray structure determination and by vibrational spectroscopy (IR, Raman) as well as by EPR spectroscopy, whereas 2b is characterized by IR spectroscopy.1: Space group P21/n, Z = 2, a = 1009.5(1), b = 1226.6(2), c = 1943.0(2) pm, β = 98.42(1)°, R1 = 0.0672. The complex anion $\rm [VOCl_{2}(\mu-N_{3})]^{2-}_{{2}/{2}}$ forms centrosymmetric units with V2N2‐four‐membered rings with a V···V distance of 335.6(1) pm and coordination number five on the vanadium(IV) atoms.2a: Space group $\rm P{\bar 1}$, Z = 1, a = 1089.0(2), b = 1097.1(2), c = 1310.1(2) pm, α = 92.99(1)°, β = 106.12(2)°, γ = 117.05(2)°, V = 1309.8(4) Å3, dcalc. = 1.440 g·cm−3, R1 = 0.0384. The complex anion forms centrosymmetric units of symmetry Ci with V2N2 four‐membered rings and VN bond lengths of 200.4(3) and 234.4(2) pm, respectively. The non‐bonding V···V distance amounts to 356.2(1) pm.2b: Space group $\rm P{\bar 1}$, Z = 1, a = 1037.3(2), b = 1157.6(2), c = 1177.2(2) pm, α = 98.48(2)°, ° = 103.82(2)°, γ = 106.33(2)°, V = 1281.8(4) Å3, dcalc. = 1.471 g·cm−3, R1 = 0.0724. The structure of the complex anion $\rm [VOCl(\mu-N_{3})(N_{3})_{2}]^{2-}_{{2}/{2}}$ is similar to the anion of 2a with VN bond lengths of the four‐membered V2N2 ring of 203.3(4) and 235.2(4) pm, respectively, and a non‐bonding V···V distance of 357.5(1) pm.