Chemistry:Vanadium(V) chloride chlorimide

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Vanadium(V) chloride chlorimide
Identifiers
3D model (JSmol)
Properties
Cl4NV
Molar mass 206.75 g·mol−1
Density 2.48
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).
Infobox references

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]

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.[5] The solid has a triclinic crsystal 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 ∠VNCl 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" (in de). Zeitschrift für anorganische und allgemeine Chemie 634 (8): 1326–1328. 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. 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): 181–181. doi:10.1007/BF00608704. 
  5. ↑ Maple, T. G. (in de). Vanadium: Teil B — Lieferung 1. Verbindungen bis Vanadium und Wismut. Springer-Verlag. p. 252. ISBN 978-3-662-13314-9. https://books.google.com/books?id=riCyBgAAQBAJ&pg=PR252. 
  6. ↑ Strähle, J.; Bärnighausen, H. (21 April 1966). "Darstellung und Kristalldaten von Vanadin-(chlorimid)-trichlorid, Cl3VNCl". Angewandte Chemie 78 (8): 450–451. doi:10.1002/ange.19660780809. 
  7. ↑ 7.0 7.1 Strähle, J.; Bärnighausen, H. (21 November 1967). "Die Kristallstruktur von Vanadium(chlorimid)trichlorid, Cl3VNCl". Angewandte Chemie 79 (22): 1020–1020. 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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