Alkoxides zirconium

Zirconium alkoxides behave similarly in regard to thermal stability. The series zirconium methoxide [28469-78-5] zirconium ethoxide [18267-08-8] zirconium isopropoxide [2171 -98 ] zirconium /r /f-butoxide [2081 -12-1] shows decreasing thermal stability. 

Zirconium Alkoxides. Like the corresponding titanium compounds, the 2irconium alkoxides are manufactured from soHd 2irconium tetrachloride and the respective alcohol in the presence of ammonia. Higher alkoxides are manufactured by alcoholysis. Zirconium -propoxide and -butoxide are commercially available in barrels at about 14/kg. 

Zirconium alkoxides are used for cross-linking and hardening of isocyanate, epoxy, siUcon, urea, melamine, and terephthalate resins in the sol-gel process as catalysts in condensation and as water repellents. Zirconium alkoxides hydroly2e in moist air, but more slowly than titanium alkoxides. 

Alkoxides. Zirconium alkoxides are part of a family of alcohol-derived compounds (219). The binary zirconium compounds have the general formula ZRX — (OR). They are easily hydrolyzed and must be prepared under anhydrous conditions. They are prepared by the reaction of zirconium tetrahahdes and alcohols ... 

Double alkoxides of zirconium with alkah metals of the type MZr2(OR) have been obtained by reaction of alkah metal alkoxides with zirconium alkoxides (220). Although these usually are monomeric derivatives, the reaction between zirconium tetra-/-butoxide [1071 -76-7] and sodium /-butoxide was found (221) to form dimeric NaZr(OC(CH2)2) ]2. 

Zirconium alkoxides readily hydrolyze to hydrous zirconia. However, when limited amounts of water are added to zirconium alkoxides, they partially hydrolyze in a variety of reactions depending on the particular alkoxide (222). Zirconium tetraisopropoxide [2171 -98-4] reacts with fatty acids to form carboxjiates (223), and with glycols to form mono- and diglycolates (224). 

Zirconium dichiorohis(dimethylamide) [87227-57-4] ZrCl2[N(CH2)2]2 h made direcdy from methylamine and zirconium tetrachloride but all of the halogens can be substituted by treating zirconium tetrachloride with the appropriate lithium alkylamide (229). Zirconium arylamines are made from zirconium alkoxides which first are converted to aryloxides (230). 

Employing silicon alkoxides, the hydrolysis has to be catalyzed by the addition of an acid or a base, and an excess of water is often used. Employing zirconium alkoxides, the hydrolysis reaction proceeds much faster than the condensation so that the product is obtained as a precipitate rather than a gel. 

Zirconium, tetrakis(acetylacetonate)-stereochemistry, 1, 32, 94 Zi rconium, tris(phenylenedithio)-structure, 1, 63 Zirconium alkoxides oligomeric structure, 2,346 Zirconium chloride... 

Mn(II) > Mg(II).270 It should be underlined that titanium and zirconium alkoxides are efficient catalysts for both stages of reaction. Lanthanide compounds such as 2,2/-bipyridyl, acetylacetonate, and o-formyl phenolate complexes of Eu(III), La(III), Sm(III), Er(III), and Tb(III) appear to be even more efficient than titanium alkoxides, Ca or Mn acetates, Sb203, and their mixtures.273 Moreover, PET produced with lanthanides has been reported to exhibit better thermal and hydrolytic stability as compared to PET synthesized with the conventional Ca acetate -Sb203 catalytic system.273... 

Ziegler-Natta catalysis, 431, 449 Zinc diacetate catalysts, 71 Zirconium alkoxides, 68... 

The zirconium alkoxides Zr(OR)4 are reported as inactive for the epoxidation of olefins under the conditions recommended with the titanium analogs. When synthesized by reaction of Zr(CH2CMe3)4 with silica, followed by hydrolysis or calcination, a solid as active as the related Ti-based catalyst is obtained. The low selectivity for the formation of the epoxide is related to the fact that the same Zr centers catalyze both the formation and the decomposition of the epoxide.46... 

Lanthanide-doped inverse photonic crystals have been reported.282 The lattices were prepared by infilling self-assembled polystyrene sphere templates with a mixture of zirconium alkoxide and europium at 450 °C, the polystyrene spheres were burnt out leaving hollow spheres of air, and the infilled material was converted to Zr02 Eu3+. The PL properties of the resulting photonic lattice were reported.282 The possibility of including phosphors into photonic lattices could lead to many... 

The chemistry of zirconium has been reviewed in COMC (1982) and COMC (1995)123 124 as well as in Comprehensive Coordination Chemistry 7/.125 Various other reviews cover applications of zirconium alkoxides,126 zirconium-phosphorous... 

The elimination from the zirconium alkoxide B (Scheme 8.23) to give the 1,4-diene also proceeds through cationic activation. An independently prepared sample of pure B (X = Cl) would not undergo elimination unless a catalytic amount of AgC104 (or TMSC104, which is the probable chain carrier in this elimination reaction) was added. If AgAsF6 is used as the promoter for the reaction sequence, only the first (addition) step takes place and no elimination to the diene is observed [51],... 

Later, Kricheldorf and coworkers extended the concept of the aluminum alkox-ide-initiated ROP of lactones to a set of other metal alkoxides such as tin(lV) [23-25], titanium, and zirconium alkoxides. As a rule, the polymerization takes place according to the same coordination-insertion mechanism shown in Fig. 12. 

Randon et al. reported on an alternative approach for the preparation of zirconia monoliths [96]. The sol-gel process is initiated by hydrolysis of an ethanolic zirconium alkoxide solution, on addition... 

Oxidation of primary, secondary and benzylic alcohols with TBHP or CHP, mainly catalyzed by Mo and Zr derivatives, were performed by different authors. As an example, Ishii, Ogawa and coworkers reported the conversion of secondary alcohols such as 2-octanol to ketones mediated by catalyst 39 and TBHP. The oxidation of cyclic alcohols depended on steric factors. Zirconium alkoxides may act as catalysts in the conversion of different alcohol typologies with alkyl hydroperoxides . Secondary alcohols, if not severely hindered, are quantitatively converted to the corresponding ketones. The selectivity for equatorial alcohols is a general feature of the system, as confirmed by the oxidation of the sole cis isomer 103 of a mixture 103-bl04 (equation 68). Esters and acids could be the by-products in the oxidation of primary alcohols. 

Peercy, P.S., Dosch, R.G., and Morosin, B., "Preparation and Structural Studies of the Hydrolysis Products of Titanium, Niobium and Zirconium Alkoxides," SAND76-O556, Sandia Laboratories, Albuquerque, NM (1976). 

On the basis of H NMR data it has not been possible to make any definite conclusions concerning the structures of oligomeric titanium and zirconium alkoxides. At room temperature only one set of CH2CH3 signals was observed for [Ti(OEt)4]4 and although the presumably rapid... 

In the case of organic derivatives such as zirconium acetate, direct bonding of the carboxyiate to the zirconium is found. Similar structures are also found in solvent-soluble, water-insoluble carboxylates such as zirconium propionate. Zirconium alkoxide derivatives tend to be monomeric in solvent-based systems but hydrolyse rapidly with ambient water to give polymeric species. 

Kobayashi and colleagues developed a catalytic enantioselective method for the allylation of imines 24 by substituted allylstannanes 25 with chiral zirconium catalysts 26 and 27 prepared from zirconium alkoxides and l,l -bi-2-naph-thol derivatives (Scheme 10) [19]. The allylation of aromatic imines 24 with 25 afforded the corresponding homoallylic amines 28 in good yields (71-85%) with high stereoselectivities (87-99% ee). 

A benzoylation of an organozirconium compound is achieved by condensation with ben-zaldehyde, followed by the in situ Oppenauer oxidation of the resulting zirconium alkoxide... 

It has been traditionally assumed that condensation is a much slower reaction than substitution of the alkoxide group by the hydroxide however, quite recendy it was shown that the rates of these processes are actually very close. Kinetic study of hydrolysis of titanium and zirconium alkoxides by means of a quick mixing technique with FIIR, SAXS, and conductivity measurements monitoring has shown that hydrolysis is a very quick reaction followed by condensation, which is also a very fast process and occurs after from 25 to 50% of alkoxide groups are substituted by hydroxides (under the experiment conditions this occurs in 80 milliseconds after the beginning of mixing of the reagents) [709]. 

---