Nitrido-und Oxochlorokomplexe des Vanadiums(V); die Kristallstruktur von AsPh₄ [V0C1₄] Nitrido and Oxochloro Complexes of Vanadium(V); the Crystal Structure of AsPh₄[VOCl₄]

Abstract

<jats:p>The complexes AsPh<jats:sub>4</jats:sub>[Cl<jats:sub>4</jats:sub>V = N-Cl] and AsPh<jats:sub>4</jats:sub>[VOCl<jats:sub>4</jats:sub>] are prepared by the reaction of AsPh<jats:sub>4</jats:sub>Cl with Cl<jats:sub>3</jats:sub>VNCl and VOCl<jats:sub>3</jats:sub>, respectively. The IR spectra indicate C<jats:sub>4v</jats:sub> symmetry for the complex anions with multiple VN and VO bonds and a linear arrangement for the VNCl-group. AsPh<jats:sub>4</jats:sub>[VOCl<jats:sub>4</jats:sub>] crystallizes in the tetragonal space group P4/n with two formula units in the unit cell. The crystal structure was solved by X-ray diffraction methods (R = 0,062, 1096 observed, independent reflexions). The structure consists of AsPh<jats:sub>4</jats:sub>+ cations and [VOCl<jats:sub>4</jats:sub>]- anions with symmetry C<jats:sub>4v</jats:sub>. The extremely short VO bond length corresponds with a VO triple; its steric requirements cause the relatively large bond angle OVCl of 103.4°.</jats:p>

Synthesis and Properties of Complexes of Vanadium(V) Oxide Trichloride with Nitrogen‐ and Oxygen‐Donor Ligands

“…Decomposition in solution is faster and, despite many attempts, X-ray quality crystals of the complexes have not proved to be obtainable. The two commonest products of hydrolysis are the dark red [VOCl 4 ] -and yellow [VO 2 Cl 2 ] -anions, [21,22] which are readily detected by 51 V NMR spectroscopy [ 51 V: [23] 99.76 %, I = 7/2, Ξ = 26.29 MHz, Q = -5.2·10 -30 m 2 , D c (receptivity relative to 13 C) = 2150], (Table 1). The 51 V chemical shift of the former is slightly solvent-dependent and lies in the range δ = +45 to +50 ppm, which is to high frequency of the resonances of 3 L} n adducts in in situ studies, [4] are in fact due to hydrolysis to [VO 2 Cl 2 ] -.…”

P(C6H5)4[VOBr4]: Synthese, IR-Spektrum und Kristallstruktur / P(C6H5)4[VOBr4]: Synthesis, IR Spectrum and Crystal Structure

“…Wegen der guten Kristallisationseigenschaften und wegen der hydrophoben Wirkung der Phenylringe haben wir als Kation das zugleich von der Größenrelation her günstige Tetraphenylphosphonium-Kation verwandt. Mit dem ähnlich großen Tetraphenylarsonium-Kation haben wir unlängst auch das AsPl^VOCU] hergestellt und kristallographisch charakterisiert [2],…”

Die Oxochlorovanadate PPh4[VOCl3OH], PPh4[VOCl4], (PPh4 )2 [VOCl4 ]·2CH3CN und (PPh4)2[VOCl4]·CH3CN mit auffälligen Abweichungen von der quadratisch-pyramidalen Anionenstruktur / The Oxochlorovanadates PPh4[VOCl3OH], PPh4[VOCl4], (PPh4 )2 [VOCl4 ]·2CH3CN and (PPh4)2[VO

“…1107, 8(2) 1254,0(2) 1281, 3(5); q = 84,11(4)°1017,1(3); a = 77,74(2)°b (pm) 1922,2 (3) 1254,0 (2) 1276, 6(4); ß = 83,95(4)°1029, 9(3); ß = 79,99 (2) (PPh4)[VOCl4] 0 (2 )-V -0 (l) 106,5 (2) O-V-Cl 103,29(5) 0 (2)-V-Cl ( 1) 103, 9(2) Cl-V-Cl'( trans) 153,41(9) 0(2)-V-Cl (2) 104, 9(2) 0(2)-V-Cl (3) 106,6(2) O (l)-V -C K l) 149,6(2) Cl(2)-V-Cl (3) 147,69 (6) …”

“…• 2 CH 3CN 0=V-C1 ( 1) 106, 8(2) 113,27(8) 0=V-C1 (2) 101, 7(1) 96.69(8) 0=V-C1 (3) 107, 3(2) 113,48(8) 0=V-C1 (4) 101, 5(1) 97,51(8) Cl(l)-V-Cl (3) 145,88 (6) 133,25(3) Cl(2)-V-Cl (4) 156,87 (6) 165,80 (3) Abb Zu 0,60 g V 2S5 (2,3 mmol), das von der Herstel lung sauerstoffhaltig war, und 1.12 g PPh4Cl (3, …”