Vanadium(V) chloride chlorimide
Chemical compound
From Wikipedia, the free encyclopedia
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]
_chloride_chlorimide_tetrahedral.png)
| |
| Identifiers | |
|---|---|
3D model (JSmol) |
|
| ChemSpider | |
| |
| |
| 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).
| |
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]