Vanadium(V) chloride chlorimide

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Vanadium(V) chloride chlorimide
Vanadium(V) chloride chlorimide tetrahedral.png
Identifiers
3D model (JSmol)
ChemSpider
  • InChI=1S/ClN.3ClH.V/c1-2;;;;/h;3*1H;/q;;;;+3/p-3
    Key: SNGARBHUIAVTIM-UHFFFAOYSA-K
  • ClN=[V](Cl)(Cl)Cl
Properties
Cl4NV
Molar mass 206.75 g·mol−1
Density 2.48 g/cm3
Melting point 136 °C (277 °F; 409 K)
log P 2.94160
Related compounds
Other anions
VOCl3; VCl5; Cl3VNBr; Cl3VNI [1]
Other cations
ReNCl4 [2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Vanadium (V) chloride chlorimide is a chemical compound containing vanadium in a +5 oxidation state bound to three chlorine atoms and with a double bond to a chlorimide group (=NCl). It has formula VNCl4. This can be also considered as a chloroiminato complex. [3]

Contents

Production

Vanadium(V) chloride chlorimide can be made by chlorinating vanadium nitride at 120°. Or chlorine azide can react with vanadium tetrachloride to yield it. Or more conveniently it can be made by heating vanadium tetrachloride with sodium azide and chlorine gas. [4]

Properties

The melting point of Vanadium(V) chloride chlorimide is 136 °C. It can be sublimed in a vacuum below its melting point. The density of the solid is 2.48 g/cm3. [5] The solid has a triclinic crystal structure with unit cell a=7.64, b=7.14, c=5.91 Å; α=112.4°, β=94.9°, γ=107.8° with Z=2 (formulas per unit cell). [6] The space group is P1. [7]

Vanadium(V) chloride chlorimide is molecular. In the gas phase the V to N bond length is 1.651 Å, V to Cl bond length is 2.138 Å, N to Cl bond length is 1.597 Å. The bond angles are ∠ClVCl 113.4°, VNCl 169.7 and ∠NVCl 106.0. [8]

In the solid form, the bond lengths are slightly different. V-Cl: 2.20, 2.30 and 2.38 Å, V=N bond is 1.64 Å long and N-Cl length is 1.59 Å. The VNC angle is 175.2°. [7]

Reactions

VCl3NCl can crystallise with antimony pentachloride. Phosphines and nitrogen bases can form complexes with the vanadium in this compound. (triphenyl phosphine, tributyl phosphine, pyridine, bipyridine). A reaction with ammonium chloride yields the [Cl5VNCl]2− ion. [9]

References

  1. ↑ Dehnicke, Kurt; Liebelt, Wolfgang (June 1979). "N-Halogen-Vanadiumnitridchloride, Cl3V≡N−X, mit X = Br, I". Zeitschrift für anorganische und allgemeine Chemie. 453 (1): 9–13. doi:10.1002/zaac.19794530603.
  2. ↑ Binder, Anja; Maichle-Mössmer, Cäcilia; Niquet, Elke; Strähle, Joachim (July 2008). "Synthese und Kristallstruktur der Rhenium(VII)-Nitridchloride ReNCl4 und ReNCl4·H2O". Zeitschrift für anorganische und allgemeine Chemie (in German). 634 (8): 1326–1328. Bibcode:2008ZAACh.634.1326B. doi:10.1002/zaac.200800057.
  3. ↑ Strähle, Joachim (September 2007). "Reactions of Transition Metal Azido Complexes and their Reaction Products". Zeitschrift für anorganische und allgemeine Chemie. 633 (11–12): 1757–1761. Bibcode:2007ZAACh.633.1757S. doi:10.1002/zaac.200700170.
  4. ↑ Fernández, V.; Dehnicke, K. (April 1975). "Eine vereinfachte Synthese und das Raman-Spektrum von Cl3VNCl". Die Naturwissenschaften. 62 (4): 181. Bibcode:1975NW.....62..181F. doi:10.1007/BF00608704. S2CID   42779188.
  5. ↑ Maple, T. G. (31 August 2013). Vanadium: Teil B — Lieferung 1. Verbindungen bis Vanadium und Wismut (in German). Springer-Verlag. p. 252. ISBN   978-3-662-13314-9.
  6. ↑ Strähle, J.; Bärnighausen, H. (21 April 1966). "Darstellung und Kristalldaten von Vanadin-(chlorimid)-trichlorid, Cl3VNCl". Angewandte Chemie. 78 (8): 450–451. Bibcode:1966AngCh..78..450S. doi:10.1002/ange.19660780809.
  7. 1 2 Strähle, J.; Bärnighausen, H. (21 November 1967). "Die Kristallstruktur von Vanadium(chlorimid)trichlorid, Cl3VNCl". Angewandte Chemie. 79 (22): 1020. Bibcode:1967AngCh..79.1020S. doi:10.1002/ange.196707922112.
  8. ↑ Oberhammer, H.; Strähle, J. (1 March 1975). "Die Molekülstruktur des Vanadium-(N-chlorimid)-trichlorids, Cl3V=NCl, und des Vanadiumoxidtrichlorids, Cl3V=O, in der Gasphase / The Gas Phase Molecular Structure of Vanadium(N-Chlorimide)Trichloride, Cl3V=NCl, and Vanadium Oxide Trichloride, Cl3V=O". Zeitschrift für Naturforschung A. 30 (3): 296–303. doi: 10.1515/zna-1975-0306 .
  9. ↑ Lörcher, K.-P.; Strähle, J.; Walker, I. (April 1979). "Das komplexchemische Verhalten des Cl3V≡N−Cl gegenüber Lewissäuren und -basen Die Kristallstruktur der Komplexe Cl3VNCl(SbCl5)2 und Cl3(bipy)VNCl". Zeitschrift für anorganische und allgemeine Chemie. 452 (1): 123–140. doi:10.1002/zaac.19794520117.
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