The vibration spectrum demonstrates that the ionic form is present exclusively [3]. The force constant of [AsCl.+]+ is somewhat higher than that of the isoelectronic GeC14. Reucrions with Cl20: Oxide chloride syntheses with C120 are a!ready familiar. ZrOClz has now been prepared at -15OC in CC14:
According to the infrared spectrum. ZrOCI2 is a zirconyl tetrachloro-oxozirconate [ZrO]2+[ZrOC14]2-with a chainform anion polymerized via the oxygen atoms. Refictions wifh CINO3: By the method of Schnieisser [4], the anhydrous nitrates Co(NO& (p = 4.85 B.M.) and M n ( N 0 3 ) ~ ([L = 5.48 B.M.) result from CoCIz and MnC12 with chlorine nitrate. Co(N03)2 forms a solvate with Nz04, which according to spectral and magnetochemical data is a nitrosyl trinitratocobaltate NOi[Co(ON02)3]-(p = 5.19 B.M.) with the nitrato group as a bidentate ligand. From the chloride fluorides SbC14F and [AsC14]+[AsF& the complex nitrates [Sb(ON02)41fF-and [As(ON02)4]'[AsF& are obtainzd with chlorine nitrate. SbF3C12 yields an unstable SbF3(0N02)2, which: is stabilized by rearrangement at 40ยฐC: SbF,(ONOz)z -+ N 0 2 + [SbOF,(ONO?)]-. Thermal decompositon of the fluoride nitrates leads to the formation of definite oxide fluorides, e.3. [As(ONOz)4]+[AsF,& + 2 ASOF] + 4 NO2 + 0:
Reactions with ClN3: SbC15 reacts with chlorine azide to form SbC14N3, which splits o f f Nz and Cl2 and is thereby converted into polymeric SbNC12. An unstable chloride azide VC14N3 is formed from VC14 and GIN,. In solution it splits otT N2 spontaneously:
The radical is stabilized by anionotropy yielding an Nchlorovanadiuni imide:
[Cl4V-g] + CI,V=N-CI This compound is monomeric, sublimes readily and melts at 132 OC in a sealed tube. The V=N double bond absorbs in the infrared at 1110 cm-1.