Mechanisms of the Reactions of Diethylzinc With Isopropanol and Water

Herold, R. J.; Aggarwal, S. L.; Neff, Volker

doi:10.1139/v63-187

Cited by 61 publications

(28 citation statements)

References 6 publications

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“…As for oxygen source, H 2 O, ozone, alcohols, O 2 , and N 2 O have been employed. In sol-gel method, the mechanism for the reaction of DEZ with isopropanol and water has been studied by Herold, et al [12]. The reaction of DEZ with water was found to proceed in a two-step manner: the evolution of ethylzinc hydroxide {Zn(C 2 H 5 )OH}, followed by its decomposition to ZnO.…”

Section: Introductionmentioning

confidence: 99%

Determination of the molecular size of growth species in the AP-MOCVD of ZnO from DEZ and H2O

Velasco¹,

Mitsuji²,

Minami³

et al. 2008

Journal of Crystal Growth

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Section: Introductionmentioning

confidence: 99%

Determination of the molecular size of growth species in the AP-MOCVD of ZnO from DEZ and H2O

Velasco¹,

Mitsuji²,

Minami³

et al. 2008

Journal of Crystal Growth

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“…Nevertheless, cryoscopic studies carried out on the controlled hydrolysis of diethylzinc show the formation of organozinc hydroxide EtZnOH as intermediate. 130,131 This intermediate, which is thought to have the dimeric structure (EtZnOH) 2 , is very unstable and reacts further to give polymers of the form Et(ZnO) n (equation 19). Some of these products exhibit a good catalytic activity for the polymerization of lactones and cyclic ethers.…”

Section: Other Organozinc Compounds Containing Oxygenmentioning

confidence: 99%

Zinc: Organometallic ChemistryBased in part on the article Zinc: Organometallic Chemistry by Gerard Parkin which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Grévy

2005

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Since the discovery of the first organozinc compounds by Sir Edward Frankland in 1849, the organometallic chemistry of zinc made remarkable advances and organozinc species have become essential tools for organic chemists. During the past decade, numerous new and modified procedures for the preparation of the title compounds have been published, rendering their synthesis easier, faster, and less expensive and giving higher yields. The coordination chemistry of organozinc derivatives has been subject of further interest and various intra‐ and intermolecular complexes with different donor ligands have been structurally characterized by X‐ray crystallography and spectroscopic methods. The accumulation of molecular structures, physicochemical studies, and computational calculations has led to a better understanding of the organozinc chemistry, and consequently to the design of new derivatives for specific applications. Even if the development of areas like the chemistry of organozinc anions and cations is still in its early stage, these compounds, which exhibit properties different than those of the parent organometallic species, appear to have promising applications in synthesis and catalytic reactions. During the past ten years, the chemistry of organo‐ gem ‐dizincio derivatives has also been the subject of much interest and progress. These reagents can form two carbon–carbon bonds in a one‐pot reaction and with high stereoselectivity. They became key reagents for organic chemists who want to combine multiple transformations in one operation. The importance of organometallic compounds of zinc can be seen in the growing number of their applications in synthesis. They are used in many reactions such as substitutions, additions to carbonyl compounds and unsaturated systems, cyclopropanations, and polymerizations. Furthermore, as a result of their low reactivity, they tolerate a wide variety of functionalities and perform most of the transformations with high regio‐ and enantioselectivity. After spending more than half a century in the shade of Grignard and organolithium reagents, organozinc reagents are becoming more and more important in modern chemistry.

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“…This is caused by the very complex polymerization process, with polymerization, depolymerization, side reactions and polymer precipitation occurring simultaneously 2) , and by the heterogeneity of the catalysts at the molecular level 17) . For instance, the diethylzinc/water system contains oligomers, Et(ZnO) x H, with different values of x 18,19) . The catalyst is actually a mixture of different molecules with many active sites, which are inter-and intramolecularly associated, involving zinc atoms with different degrees of coordination.…”

Section: Copolymerization Of Mesogenic Epoxides and Comentioning

confidence: 99%

Synthesis and characterization of novel side-chain liquid crystalline polycarbonates, 4. Synthesis of side-chain liquid crystalline polycarbonates with mesogenic groups having tails of different lengths

Jansen¹,

Addink

Nijenhuis

et al. 1999

Macromol. Chem. Phys.

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SUMMARY: Side-chain liquid crystalline polycarbonates with alkoxyphenylbenzoate side groups, having a short spacer and tails ranging from 1 to 8 C-atoms, were synthesized. The polymers were prepared by an organo-zinc catalysed copolymerization of carbon dioxide and mesogenic 4-alkoxyphenyl 4-(2,3-epoxypropoxy)benzoates. Model polycarbonates were prepared by copolymerization of glycidyl phenyl ether (GPE) and carbon dioxide and by terpolymerization of GPE, propylene oxide and CO 2 . The copolymerizations of LC monomers were carried out at 70 8C in an autoclave at 60 atm CO 2 pressure in dioxane as the solvent. Catalysts based on diethylzinc and water or diethylzinc and resorcinol were used. High catalyst concentrations (up to 20 mol-% on the basis of diethylzinc with respect to epoxide) and long reaction times (72 h) were found to be necessary for acceptable yields and reasonable molar masses. The resulting polymers had a high polydispersity and the maximum yield was about 30%. A major side product, formed directly from CO 2 and epoxide, as well as indirectly by depolymerization, was the corresponding five-membered cyclic carbonate. The polymers on average contained about 30 mol-% of ether units and 70 mol-% of carbonate units due to a weak tendency of the epoxides to undergo homopolymerization. 1 H and 13 C NMR analysis revealed detailed information about the overall ether content and the distribution of the ether and carbonate groups in the chain, as well as the tacticity of the polymers. Surprisingly, the monomer distribution and the tacticity were molecular weight dependent. Some possible explanations for these phenomena are suggested.

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Mechanisms of the Reactions of Diethylzinc With Isopropanol and Water

Cited by 61 publications

References 6 publications

Determination of the molecular size of growth species in the AP-MOCVD of ZnO from DEZ and H2O

Determination of the molecular size of growth species in the AP-MOCVD of ZnO from DEZ and H2O

Zinc: Organometallic ChemistryBased in part on the article Zinc: Organometallic Chemistry by Gerard Parkin which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Synthesis and characterization of novel side-chain liquid crystalline polycarbonates, 4. Synthesis of side-chain liquid crystalline polycarbonates with mesogenic groups having tails of different lengths

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