Zirconium trichloride

Lower Valent Halides. Zirconium trichloride [10241-03-9], ZrCl, tribromide [24621 -18-9], ZrBr, and triiodide [13779-87-8], Zrl, are... 

Zinc iodide, 4632 Zirconium(II) chloride, 4121 Zirconium dibromide, 0285 Zirconium tetrachloride, 4178 Zirconium tetraiodide, 4639 Zirconium trichloride, 4160... 

Zinc iodide, 4627 Zirconium dibromide, 0284 Zirconium tetrachloride, 4172 Zirconium tetraiodide, 4634 Zirconium trichloride, 4154 Zirconium(II) chloride, 4115 See also METAL PNICTIDES... 

The reactivity of the zirconium trichloride 419 bearing a chlorodimethylsilyl-substituted Cp ligand toward various nucleophilic reagents has been extensively investigated. As with 416, the reactions of 419 with lithium amides in hexane produce diverse products. For example, its reaction with 1 equiv. of LiN(SiMe3)2 gives the monoamido... 

The reaction of bis(3,5-dimethylpyrazol-l-yl)methyl lithium and 6,6-diphenylfulvene generates the lithium salt of a tridentate hybrid Cp/scorpionate ligand 443, and the subsequent metathesis reaction with ZrCL leads to the six-coordinate zirconium trichloride 444 (Scheme 100).313 Both the lithium and zirconium complexes were crystallographically characterized. 

The salt metathesis reaction of ZrCU and the lithium tetramethylcyclopentadienide bearing the 2-methoxyethyl or the 2-methylthioethyl donor sidearm produces half-sandwich zirconium trichloride complexes 445 (Equation (34)).314,315 As expected, these complexes show monomer-dimer dynamic behavior in solution and exist as doubly chloro-bridged dimers in the solid state. 

Newnham and Watts 391) were successful in producing high-purity zirconium trichloride, tribromide, and triiodide from the corresponding tetrahalides by atomic hydrogen reduction in a glow discharge tube. A yield of about 0.5 gm/hour was obtained. The product was separated from unreacted tetrahalide by sublimation at 200°C for the chloride and bromide, and 260°C for the iodide under reduced pressure. Careful control of flow rates, temperature, and electrode design are required for the successful operation of this process. 

The melting point of pure zirconium trichloride could not be obtained because of disproportionation. Attempts to determine the phase diagram for the sodium chloride system failed because of excessive disproportionation. In the potassium chloride-zirconium trichloride system the eutectic temperature was 581° 2°C. A mixed system was used, however, since it was found that the stability of the trichloride was satisfactory in a 50 50 sodium chloride potassium chloride melt. Powder patterns of the frozen melt at 15 mole% zirconium trichloride which had been at 750°C for 24 hours showed no evidence of the dichloride and tetrachloride. There was evidence for slight solubility of the trichloride in the solid at this composition. The reaction of zirconium metal with the trichloride in the equimolar sodium-potassium chloride melt revealed that even after the trichloride had been reduced to the dichloride, zirconium metal dissolved to the extent of 5 x lO" or 10 mole fraction of excess metal in the solution. Zirconium metal did not, however, appear to dissolve in the melt in the absence of zirconium dichloride. 

From the study of cell potentials, the equilibrium constants for various reductions in the equimolar sodium-potassium chloride melt were calculated 550) (Table XXVII). The high values of the equilibrium constants indicate that zirconium metal should reduce any tetravalent or trivalent zirconium present to the divalent species. The reduction in both cases should he quantitative. It can also be predicted that zirconium trichloride in solution does not disproportionate to any significant extent, and that the reaction between zirconium dichloride and tetrachloride to produce zirconium trichloride proceeds almost to completion. 

Hi. Absorption spectra. The diffuse reflection spectrum of zirconium trichloride reported by Clark (108) shows an intense band at 17,300 cm with a shoulder at 21,000 cm which is interpreted as a ligand-... 

ZnBr2[g] ZINC BROMIDE (GAS) 1831 ZrCI3 ZIRCONIUM TRICHLORIDE 1863... 

ZnC03 ZINC CARBONATE 1831 ZrCI3[g] ZIRCONIUM TRICHLORIDE (GAS) 1864... 

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