Ethylzinc Complexes Research Articles

From Uncommon Ethylzinc Complexes Supported by Ureate Ligands to Water-Soluble ZnO Nanocrystals: A Mechanochemical Approach

Urea and its derivatives, due to their unusual versatility of coordination modes to metal centers and the presence of multiple hydrogen-bond donor sites, are widely utilized as neutral or monoanionic ligands in coordination and bioinorganic chemistry and as building units of bioinspired materials. However, metal complexes with ureate ligands have essentially not been applied as precursors of hybrid organic–inorganic nanomaterials. We report on the synthesis and structure characterization of two novel organozinc ureate complexes incorporating N-phenylureate or N,N′-dicyclohexylureate ligands, the latter being the first reported complex with the μ3-μ2(O):κ1(N) ureate coordination mode. These findings not only expand the horizon of urea–zinc chemistry but also pave the way for efficient bottom-up mechanochemical synthesis of sub-10 nm diameter zinc oxide nanocrystals (ZnO NCs) coated by the ureate ligands. We explored the NC formation triggered by mechanical force from both a well-defined monocrystalline precursor and an insoluble hard-to-process amorphous organozinc precursor. Moreover, the organic shell of the N-phenylureate-coated ZnO NCs was modified via a facile, fast, and solventless host–guest complexation with β-cyclodextrin using a mechanochemical approach, which afforded water-soluble ZnO NCs. The reported procedure is the first example of rapid and sustainable mechanochemical synthesis of hybrid nanomaterials from organometallic precursors.

Zinc Complexes of Sequential Tetradentate Monoanionic Ligands in the Isoselective Polymerization of rac-Lactide.

Zinc complexes of {ONNN}-type sequential tetradentate monoanionic ligands reacted with diethylzinc to give the mononuclear ethylzinc complexes. The benzyloxy complexes were formed readily and were found to be highly active as well as living/immortal catalysts for ring-opening polymerization of rac-lactic acid with a clear isospecific inclination. Chiral gas chromatography analysis revealed a mild preference for a given lactide enantiomer by the chiral catalysts.

Fluorinated triazapentadienyl ligand supported ethyl zinc(ii) complexes: reaction with dioxygen and catalytic applications in the Tishchenko reaction.

Ethyl zinc complexes [N{(C3F7)C(Dipp)N}2]ZnEt, [N{(C3F7)C(Cy)N}2]ZnEt, [N{(CF3)C(2,4,6-Br3C6H2)N}2]ZnEt and [N{(C3F7)C(2,6-Cl2C6H3)N}2]ZnEt have been synthesized from the corresponding 1,3,5-triazapentadiene and diethyl zinc. X-ray data show that [N{(C3F7)C(Dipp)N}2]ZnEt has a distorted trigonal planar geometry at the zinc center. The triazapentadienyl ligand binds to zinc in a κ(2)-mode. The zinc-ethyl bonds of [N{(C3F7)C(Dipp)N}2]ZnEt, [N{(C3F7)C(Cy)N}2]ZnEt, [N{(CF3)C(2,4,6-Br3C6H2)N}2]ZnEt and [N{(C3F7)C(2,6-Cl2C6H3)N}2]ZnEt readily undergo oxygen insertion upon exposure to dry air to produce the corresponding zinc-ethoxy or zinc-ethylperoxy compounds. The ethoxy zinc adducts {[N{(CF3)C(2,4,6-Br3C6H2)N}2]ZnOEt}2 and {[N{(C3F7)C(2,6-Cl2C6H3)N}2]ZnOEt}2 as well as the ethylperoxy zinc adduct {[N{(C3F7)C(Cy)N}2]ZnOOEt}2 have been isolated and fully characterized by several methods including X-ray crystallography. They feature dinuclear structures with four-coordinate zinc sites and bridging-ethoxy or -ethylperoxy groups. The ethyl zinc complexes catalyze the Tishchenko reaction of benzaldehyde under solventless conditions affording benzyl benzoate. The reaction of ethyl zinc complexes with dioxygen and their catalytic behaviour in the Tishchenko reaction are affected by the electronic and steric factors of the triazapentadienyl ligand. {[N{(C3F7)C(Cy)N}2]ZnOOEt}2 is an excellent reagent for the epoxidation of trans-chalcone.

Di‐nuclear zinc complexes containing tridentate imino‐benzotriazole phenolate derivatives as efficient catalysts for ring‐opening polymerization of cyclic esters and copolymerization of phthalic anhydride with cyclohexene oxide

ABSTRACTZinc catalysts incorporated by imino‐benzotriazole phenolate (IBTP) ligands were synthesized and characterized by single‐crystal X‐ray structure determinations. The reaction of the ligand precursor (C1DMeIBTP‐H or C1DIPIBTP‐H) with diethyl zinc (ZnEt2) in a stoichiometric proportion in toluene furnished the di‐nuclear ethyl zinc complexes [(μ‐C1DMeIBTP)ZnEt]2 (1) and [(μ‐C1DIPIBTP)ZnEt]2 (2). The tetra‐coordinated monomeric zinc complex [(C1PhIBTP)2Zn] (3) or [(C1BnIBTP)2Zn] (4) resulted from treatment of C1PhIBTP‐H or C1BnIBTP‐H as the pro‐ligand under the similar synthetic method with ligand to metal precursor ratio of 2:1. Single‐crystal X‐ray diffraction of bimetallic complexes 1 and 2 indicates that the C1DMeIBTP or C1DIPIBTP fragment behaves a NON‐tridentate ligand to coordinate two metal atoms. Catalysis for ring‐opening polymerization (ROP) of ε‐caprolactone (ε‐CL), β‐butyrolactone (β‐BL), and lactide (LA) of complexes 1 and 2 was systematic studied. In combination with 9‐anthracenemethanol (9‐AnOH), Zn complex 1 was found to polymerize ε‐CL, β‐BL, and L‐LA with efficient catalytic activities in a controlled character. This study also compared the reactivity of these ROP monomers with different ring strains by Zn catalyst 1 in the presence of 9‐AnOH. Additionally, Zn complex 1 combining with benzoic acid was demonstrated to be an active catalytic system to copolymerize phthalic anhydride and cyclohexene oxide. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 714–725

Ring-opening polymerization of cyclic esters by phenoxy-thioether complexes derived from biocompatible metals

A series of novel Mg(II) and Zn(II) complexes of the form LMX or L2M, supported by phenoxy-thioether ligands bearing different substituents at the ortho position of the thiophenol rings [L(-) = 4,6-tBu2-OC6H2-2-CH2S(2-R-C6H4)(-)] [M = Zn, R = H, X = N(SiMe3)2 (1) and X = Et (2); M = Mg, X = n-Bu, R = H (3), R = CH3 (4), R = Br (5); M = Mg, R = H (6)], were synthesized and characterized. Reaction of the proper zinc precursor (Zn[N(SiHMe2)2]2 or ZnEt2) with one equivalent of the phenoxy-thioether proligand produced the corresponding amido (1) and ethyl (2) zinc complexes in high yields. The monoalkylmagnesium complexes (3-5) were all obtained by butane elimination reaction of the dialkylmagnesium reagent, Mg(n-Bu)2, with one equivalent of the proligand in good yields. The homoleptic complex 6 was obtained by reaction of 0.5 equivalent of Mg(n-Bu)2 and the proper proligand. Variable temperature (1)H NMR studies performed on 2 and 3 demonstrated that the named complexes are involved in fluxional processes concerning a fast conformational change of the six-membered metallacycle. DOSY (Diffusion Ordered SpectroscopY) (1)H experiments and ligand scrambling strongly suggested that complexes 1-6 exist as dimeric species in solution. All complexes were active as catalysts in the ring-opening polymerization of cyclic esters. In particular, magnesium complexes showed superior ε-caprolactone and lactide ROP behavior in terms of activity, control of molecular weights and molecular weight distributions.

Al and Zn complexes bearing N,N,N-tridentate quinolinyl anilido-imine ligands: synthesis, characterization and catalysis in l-lactide polymerization

Reactions of N,N,N-tridentate quinolinyl anilido-imine ligands with AlMe(3) afford mononuclear aluminum complexes {κ(3)-[{2-[ArN=C(H)]C(6)H(4)}N(8-C(9)H(6)N)]}AlMe(2) (Ar = 2,6-Me(2)C(6)H(3) (1a), 2,6-Et(2)C(6)H(3) (1b), 2,6-(i)Pr(2)C(6)H(3) (1c)) or dinuclear complexes AlMe(3){κ(1)-[{2-[ArN=C(H)C(6)H(4)]N(8-C(9)H(6)N)}-κ(2)]AlMe(2) (R = 2,6-Me(2)C(6)H(3) (2a), 2,6-Et(2)C(6)H(3) (2b), 2,6-(i)Pr(2)C(6)H(3) (2c)) depending on the ratios of reactants used. Similar reactions of ZnEt(2) with these ligands give the monoligated ethyl zinc complexes {κ(3)-[{2-[ArN=C(H)]C(6)H(4)}N(8-C(9)H(6)N)]}ZnEt (Ar = 2,6-Me(2)C(6)H(3) (3a), 2,6-Et(2)C(6)H(3) (3b), 2,6-(i)Pr(2)C(6)H(3) (3c)) or bisligated complexes {κ(3)-[{2-[ArN=C(H)]C(6)H(4)}N(8-C(9)H(6)N)]}Zn{κ(2)-[{2-[ArN=C(H)]C(6)H(4)}N(8-C(9)H(6)N)]} (Ar = 2,6-Me(2)C(6)H(3) (4a), 2,6-Et(2)C(6)H(3) (4b), 2,6-(i)Pr(2)C(6)H(3) (4c)). These complexes were well characterized by NMR and the structures of 1a, 2a, 2c, 3b and 4c were confirmed by X-ray diffraction analysis. The aluminum and zinc complexes were tested to initiate lactide polymerization in which the zinc complexes show moderate to high activities in the presence of benzyl alcohol.

Unusually Stable Chiral Ethyl Zinc Complexes: Reactivity and Polymerization of Lactide

Chiral diaminophenoxy proligands, H(NNR′OR), where R = t-Bu, H and R′ = Me, H, have been developed and their respective zinc ethyl complexes, (NNR′OR)ZnEt, 3a (R = t-Bu, R′ = Me), 3b (R = H, R′ = Me), 3c (R = t-Bu, R′ = H), have been synthesized. The reactivity of 3a with alcohols was explored in detail and compared to a compound reported by Hillmyer, Tolman et al., LZnEt (L = 2,4-di-tert-butyl-6-{[(2′-dimethylaminoethyl)methylamino]-methyl}phenolate). Unlike LZnEt, 3a was inert toward ethanol (as well as methanol, isopropanol, and water). It reacted with phenol and with hydrochloric acid to form (NNMeOtBu)ZnOPh, 4a, and (NNMeOtBu)ZnCl, 5a, respectively. Racemic and enantiopure forms of 4a, (±)-4a and (R,R)-4a, were synthesized. The phenoxide complex catalyzed the ring opening polymerization of lactide to atactic poly(lactic acid).

Bimetallic Calcium and Zinc Complexes with Bridged β-Diketiminate Ligands: Investigations on Epoxide/CO2 Copolymerization

A series of dinucleating bis(β-diketiminate) ligands with rigid bridges has been prepared. In all cases the β-diketiminate unit is 2,6-iPr2C6H3NC(Me)C(H)C(Me)N-(bridge), and the bridges are either para-phenylene, meta-phenylene or 2, 6-pyridylene (the dinucleating ligands are abbreviated as PARA-H2, META-H2 and PYR-H2, respectively). These ligands have been converted to heteroleptic bimetallic calcium and zinc complexes. For calcium, only the PARA-phenylene bridged ligand led to a heteroleptic bimetallic calcium amide complex PARA-[CaN(SiMe3)2·THF]2. For the other ligands, homoleptic complexes have been isolated: META-Ca and PYR-Ca. For zinc, the whole range of heteroleptic amides could be isolated: PARA-[ZnN(SiMe3)2]2, META-[ZnN(SiMe3)2]2, and PYR-[ZnN(SiMe3)2]2. Analogue ethylzinc complexes have been prepared in quantitative yields: PARA-(ZnEt)2, META-(ZnEt)2, and PYR-(ZnEt)2. Reactions of the ethylzinc complexes with SO2 gave access to the ethylsulfinate complexes META-(ZnO2SEt)2 and PYR-(ZnO2SEt)2; fo...

Aluminum and zinc complexes supported by functionalized phenolate ligands: Synthesis, characterization and catalysis in the ring-opening polymerization of ε-caprolactone and rac-lactide

A series of aluminum and zinc complexes supported by functionalized phenolate ligands were synthesized and characterized. Reaction of 2-(3,5-R 2C 3N 2)C 6H 4NH 2 (R = Me, Ph) with salicylaldehyde or 3,5-di- tert-butylsalicylaldehyde afforded 2-((2-(1H-pyrazol-1-yl)phenylimino)methyl)phenol derivatives 2a– 2d. Treatment of 2a– 2d with an equiv. of AlR 2 3 (R 2 = Me, Et) gave corresponding aluminum aryloxides 3a– 3e, while reaction with an equiv. of ZnEt 2 afforded zinc aryloxides 4a– 4d. Treatment of 2c with 0.5 equiv. of ZnEt 2 formed diphenolato zinc complex 5. All new compounds were characterized by 1H and 13C NMR spectroscopy and elemental analyses. The structures of complexes 3a, 4a and 5 were further characterized by single crystal X-ray diffraction techniques. The catalytic activity of complexes 3– 5 toward the ring-opening polymerization of ε-caprolactone was studied. The zinc complexes ( 4a– 4d) exhibited higher catalytic activity than the aluminum complexes ( 3a– 3e). The diphenolato zinc complex 5 showed lower catalytic activity than the ethylzinc complexes 4a– 4d. The aluminum complex ( 3b) is inactive to initiate the ROP of rac-lactide, while the zinc complex ( 4d) is active initiator for the ROP of rac-lactide, giving atactic polylactide.

Lithium, Magnesium, and Zinc Iminophosphorano(8-quinolyl)methanide Complexes: Syntheses, Characterization, and Activity in ε-Caprolactone Polymerization

Lithiation of R2P(CH2C9H6N-8)NBut (R = Ph, 3; R = Pri, 4) with an equivalent of BunLi afforded lithium iminophosphorano(8-quinolyl)methanide [Li{CH(8-C9H6N)P(Ph2)NBut}(THF)] (5) and [Li{CH(8-C9H6N)P(Pri2)NBut}]2 (6), respectively. Reaction of 4 with Et2Mg yielded magnesium iminophosphorano(8-quinolyl)methanide complex (7). Treatment of 6 with ZnCl2 gave [Zn(Cl){CH(8-C9H6N)P(Pri2)NBut}] (8), which was transformed into alkylated zinc complexes [Zn(R1){CH(8-C9H6N)P(Pri2)NBut}] (R1 = Ph, 9; R1 = Me, 10) by treating with R1Li or R1MgX. Ethylzinc complexes [Zn(Et){CH(8-C9H6N)P(R2)NBut}] (R = Ph, 11; R = Pri, 12) were obtained by reaction of 3 or 4 with an equivalent of Et2Zn. Compounds 2 and 4−12 were characterized by 1H, 13C{1H}, and 31P{1H} NMR spectroscopy and elemental analyses. Structures of complexes 6−8 and 10 were further characterized by single-crystal X-ray diffraction techniques. The catalytic behaviors of complexes 7 and 9−12 in the ring-opening polymerization of ε-caprolactone was studied. Complex 7 exhibited high catalytic activity in the presence or absence of benzyl alcohol. Complexes 9−12 catalyzed the ring-opening polymerization of ε-CL in the presence of benzyl alcohol and exhibited first-order dependence on monomer concentration.

Syntheses of aluminum and zinc alkyl complexes of a highly fluorinated tris(pyrazolyl)borate using [HB(3,5-(CF3)2Pz)3]Ag(THF) as the ligand transfer agent.

Dimethylaluminum or ethylzinc complexes of highly fluorinated tris(pyrazolyl)borate ligand [HB(3,5-(CF(3))(2)Pz)(3)](-) can be obtained in excellent yield from the reaction between the silver adduct [HB(3,5-(CF(3))(2)Pz)(3)]Ag(THF) and the metal alkyl reagent Me(3)Al or Et(2)Zn. The X-ray crystal structure of [HB(3,5-(CF(3))(2)Pz)(3)]AlMe(2) shows that the tris(pyrazolyl)borate ligand coordinates to the aluminum center in kappa(2)-fashion. [HB(3,5-(CF(3))(2)Pz)(3)]ZnEt features the typical kappa(3)-bonded ligand.

ChemInform Abstract: Mixed Methyl‐ and Ethylzinc Complexes with Diethylselenocarbamate: Novel Precursors for ZnSe.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Mixed methyl and ethylzinc complexes with diethylselenocarbamate: novel precursors for zinc selenide

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTMixed methyl and ethylzinc complexes with diethylselenocarbamate: novel precursors for zinc selenideM. Azad Malik and Paul O'BrienCite this: Chem. Mater. 1991, 3, 6, 999–1000Publication Date (Print):November 1, 1991Publication History Published online1 May 2002Published inissue 1 November 1991https://doi.org/10.1021/cm00018a007RIGHTS & PERMISSIONSArticle Views103Altmetric-Citations43LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (317 KB) Get e-Alerts Get e-Alerts