NEW OXOZIRCONIUM(IV) ARYLOXIDES
253
complexes of oxygen donor ligands. XV. Oxozirconium(IV)
complexes of 1,10-phenanthroline mono N-oxide. J. Inorg.
Nucl. Chem. 1981, 43, 2144.
dissolved in methanol (30 mL) was mixed with a solution of
zirconium oxychloride (3.00 g, 16.8 mmol) dissolved in the
same solvent (40 mL) followed by the addition of triethylamine
(1.69 g, 16.8 mmol). The reaction mixture was stirred at room
temperature for about 3–4 hours, when a bright yellow solid
separated out. The solid so obtained was filtered, washed 2–
3 times with methanol and finally dried under vacuum. Yield
of ZrOCl(OC6H4NO2-4), 3.36 g (72%).
3. Agarwal, R. K.; Srivastva, A. K.; Srivastva, T. N. Studies on thor-
ium(IV) and zirconium(IV) complexes of oxygen donor ligands:
Part VII. Oxozirconium(IV) complexes of triphenylphosphine
oxide (TPPO). Ind. J. Chem. 1979, 18A, 459–461.
4. Fathima, N. N.; Balaraman, M.; Rao, J. R.; Nair, B. U. Effect of
zirconium(IV) complexes on the thermal and enzymatic stability
of Type I collagen. J. Inorg. Biochem. 2003, 95, 47–54.
5. Lue, Q. F.; Chen, D. R.; Jiao, X. L. Synthesis of long ZrTiO4
fibers by a sol-gel process free of organic components. J. Mat.
Chem. 2003, 13, 1127–1131.
From the filtrate, the quantitative amount of triethylamine
hydrochloride identified by its mp: 2608C (lit.[18] 2618C) was
isolated by evaporation to dryness. A similar procedure was
adopted for the synthesis of ZrOCl(OC6H4Cl-2) by reacting
the components viz. ZrOCl2, 2- chlorophenol and triethylamine
in 1:1:1 molar ratio.
6. Singh, D. K.; Singh, S.; Srivastva, B. Synthesis, characterization
and ion exchange properties of zirconium(IV) triethylammonium
phosphate. Ind. J. Chem. 2002, 41A, 2526–2529.
7. Bradley, D. C.; Mehrotra, R. C.; Gaur, D. P. Metal Alkoxides;
Academic Press: New York, 1978, pp. 20–21.
Preparation of Double Phenoxides, Na2[ZrO(OAr)4]
(OAr 5 OC6H4NO2-4 or OC6H4Cl-2)
8. Clark, G. R.; Nielson, A. J.; Rickard, C. E. F. Sterically congested
tris(phenoxide) complexes of tantalum(V). The X-Ray crystal
structures of [TaCl2(2,6-di-tbutylphenoxide)3] and [Ta2Cl(m-
Cl)2(2,6-Di-isopropylphenoxide)5(m-O)]. Polyhedron 1987, 6,
1765–1774.
A typical procedure adopted for the preparation of double
phenoxides of the composition Na2[ZrO(OC6H4NO2-4)4]
consists of mixing a solution of NaOC6H4NO2-4, (1.0 g,
6.2 mmol) in a mixture of tetrahydrofuran/methanol (1:1)
(20 mL) with a suspension of ZrO(OC6H4NO2-4)2, (1.20 g,
3.1 mmol) in the same solvent mixture (20 mL). The reaction
mixture was vigorously stirred for 4–5 hours at room tempera-
ture when solids appeared to go into solution. The resulting
solution was then refluxed for about 2 hours to ensure the com-
pletion of reaction. The volume of the solution was then
reduced to about one third of its original volume by evapor-
ation under vacuum. The remaining concentrated solution
was treated with petroleum ether (bp: 608C) when a colored
solid compound was obtained which was separated by fil-
tration, washed with ether (bp: 328C) and finally dried under
vacuum. The stoichiometric composition of the product was
established by elemental analyses (Table 1). Yield of Na2
[ZrO(OC6H4NO2-4)4, 1.76 g (80%). A similar procedure was
adopted for the preparation of the double phenoxide of the
composition Na2[ZrO(OC6H4Cl-2)4].
9. Fay, R. C. Zirconium and hafnium. Coord. Chem. Rev. 1982, 45,
41–66.
10. Shah, A.; Singh, A.; Mehrotra, R. C. Synthesis, characterization
and adduct formation of chloro-2,4,6-trimethylphenoxide deriva-
tives of titanium and zirconium. Polyhedron 1986, 5, 1285–1290.
11. Barraclough, C. G.; Bradley, D. C.; Lewis, J.; Thomas, I. M. The
infrared spectra of some metal alkoxides, trialkylsilyloxides, and
related silanols. J. Chem. Soc. 1961, 2601–2605.
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285–316.
13. Fay, R. C. Zirconium and hafnium. Coord. Chem. Rev. 1986, 71,
113–138.
14. Gatehouse, B. M.; Lloyd, D. J. Crystal structure of potassium
metazirconate, K2ZrO3, and its tin analog, K2SnO3. J. Solid
State Chem. 1970, 2 (3), 410.
15. Reddy, V. B.; Mehrotra, P. N. Preparation, IR and thermal studies
of calcium zirconyl oxalate. J. Inorg. Nucl. Chem. 1981, 43, 1078.
16. Gangadevi, T.; Rao, M. S.; Narayanan Kutty, T. R. Thermal
decomposition of zirconyl oxalates. Part III. Strontium and
calcium zirconyl oxalates. Ind. J. Chem. Sect. A. 1980, 19 (A),
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