The reactions of nickel(II) carboxylates with a series of ethylaluminum chlorides

The distribution of nickel in the reaction products from the reactions of nickel(II) stearate with diethylaluminum chloride (Et₂AlCl), ethylaluminum sesquichloride (Et₃Al₂Cl₃), and ethylaluminum dichloride (EtAlCl₂) in benzene was investigated as a function of the Al/Ni reaction stoichiometry. The products consist of benzene-soluble nickel complexes and a precipitate from which can be extracted NiCl₂ and metallic nickel. The percentage of each product is seen to be dependent upon the Al/Ni reaction ratio and the aluminum compound employed in the reaction. It was found that in each case six alkylaluminums are required for complete reaction with one nickel(II) stearate molecule. The compunds Et₂AlCl, Et₃Al₂Cl₃, and EtAlCl₂ were all found to have greater reducing ability than Et₃Al at room temperature. Alternative interpretations of the chloro compounds' greater reducing abilities are discussed.     

Role of added Lewis base and alkylaluminum halide on living cationic polymerization of vinyl ether

In the living cationic polymerization of isobutyl vinyl ether (IBVE) by the CH₃CH (OiBu) OCOCH₃ ( 1 )/EtAlCl₂ initiating system in the presence of the added base in hexane at +40°C, the stability of the initiating system 1 /EtAlCl₂, which form initiating species CH₃CH^⊕ (OiBu) derived from 1 , was investigated. In the presence of the Lewis base such as ethyl acetate or 1,4-dioxane, the active species was stable for 300 min even at +40°C in the absence of IBVE, and the living polymers were quantitatively obtained by adding IBVE. However, the active species was partly consumed by side reactions during the standing time for 60 min in the presence of a less basic additive such as ethyl benzoate, and about 50% of the active species was deactivated in the presence of methyl chloroacetate. Consequently, in the case of a less basic additive such as methyl chloroacetate (which was effective for the fast living polymerization), it can be seen that the careful selection of polymerization conditions was required. The living polymerization rate was dependent on the second order of EtAlCl₂ concentration. EtAlCl₂ induced the cleavage of 1 into CH₃CH^⊕ (OiBu) and EtAl^?Cl₂(OCOCH₃), and the reactivity of CH₃CH^⊕ (OiBu) and propagating carbocation may be controlled by EtAl^?Cl₂(OCOCH₃) with the aid of other EtAlCl₂. Et_1.5AlCl_1.5 exists as a bimetallic complex of EtAlCl₂ and Et₂AlCl, and it is expected that the polymers having a bimodal molecular weight distribution will be obtained due to two kinds of counteranions coming from EtAlCl₂ and Et₂AlCl. However, in the cationic polymerization of IBVE by 1 /Et_1.5AlCl_1.5 in the presence of ethyl acetate, the living polymer exhibiting a unimodal and very narrow molecular weight distribution was obtained. Thereby, it was suggested that the counteranions, EtAl^?Cl₂(OCOCH₃) and Et₂Al^?Cl(OCOCH₃), exchange rapidly with each other. © 1994 John Wiley & Sons, Inc.     

Asymmetric Diels–Alder reactions of optically active oxazolidinone-derived vinylsulfonamides

Chiral vinylsulfonamides bearing an oxazolidin-2-one moiety derived from (R)-2-phenylglycinol and (1R,2S)-norephedrine have been employed as dienophiles in asymmetric Diels–Alder reactions at normal pressure affording d.e.s of up to 99% when EtAlCl₂ or Et₂AlCl were employed as Lewis acids. Theoretical calculations justify the observed enantio- and diastereoselectivity.     

Synthesis and transformations of metallacycles. 28. Reactions of allenes with EtAlCl2 and Et2AlCl catalyzed by Ti and Zr complexes

Catalytic cycloalumination of allenes with EtAlCl₂ in the presence of Ti or Zr complexes afforded methylidene- and alkyl(benzyl)idenealuminacyclopropanes and the corresponding aluminacyclopentanes, which were identified by analyzing the hydrolysis products. The reactions with the use of Et₂AlCl instead of EtAlCl₂ produced 1,2- and 1,4-dialuminum compounds.     

NNNO-Heteroscorpionate nickel (II) and cobalt (II) complexes for ethylene oligomerization: the unprecedented formation of odd carbon number olefins

The unprecedented observation of odd carbon number olefins is reported during nickel- catalyzed ethylene oligomerization. Two complexes based on Co (II) and Ni (II) with novel tetradentate heteroscorpionate ligand have been synthesized and fully characterized. These complexes showed the ability to oligomerize ethylene upon activation with various organoaluminum compounds (Et₂AlCl, Et₃Al₂Cl₃, EtAlCl₂, MMAO). Ni (II) based catalytic systems were sufficiently more active (up to 1900 kg·mol (Ni)⁻¹·h⁻¹·atm⁻¹) than Co (II) analogs and have been found to be strongly dependent on the activator composition. The use of PPh₃ as an additive to catalytic systems resulted in the increase of activity up to 4,150 kg·mol (Ni)⁻¹·h⁻¹·atm⁻¹ and in the alteration of selectivity. All Ni (II) based systems activated with EtAlCl₂ produce up to 5 mol. % of odd carbon number olefins; two probable mechanisms for their formation are suggested – metathesis and β-alkyl elimination.     

Role of Water in the Catalysis of Ethylene Di- and Oligomerization and Toluene Alkylation Reactions Based on Nickel Bis(Acetylacetonate) Systems

It is established that the turnover frequency and number of Ni(acac)₂–50Et₂AlCl or Ni(acac)₂–50Et₂AlCl · EtAlCl₂-based systems in ethylene oligomerization processes depend on the concentration of the water in toluene. The possibility of the alkylation of toluene, used as a solvent under the considered reaction condition, is shown. The main reactions describing the role of water at the stage of the formation and functioning of catalytically active hydride nickel complexes are proposed.     

New Catalyst System,FeCI3-Et3-nAICIn (n=1, 2), for the Alternating Copolymerization of Butadiene-1,3 with Acrylonitrile

Abstract

Butadiene-1, 3 and acrylonitrile were copolymerized by alkylaluminum halides and ferric chloride systems. The efficiency of the aluminum components of these systems appears to decrease in the following order: Et₂AlCl < EtAlCl₂ < Et₃Al. Effective catalysts were not necessarily dependent on the mixing orders of the catalyst and monomers. It was found that different feed ratios between two monomers, which were varied over a wide range, always resulted in the formation of 1:1 copolymer. In order to investigate the initiation and propagation reactions, electron paramagnetic resonance was measured and a polarographic method was used on the reduction reaction of ferric chloride with organoaluminum halides in acetonitrile.     

Neutral palladium(II) complexes with P,N Schiff-base ligands: Synthesis, characterization and catalytic oligomerisation of ethylene

New N-functionalised 2-phosphinobenzaldimino (P^N) ligands bearing 3-picolyl, furfuryl, thiophene-2-methyl, thiophene-2-ethyl, and benzyl groups have been prepared in good yield. The 2-phosphinobenzaldimino ligands were reacted with PdCl₂(COD) to give the corresponding metal complexes of the type Pd(L)Cl₂ (L = 2-phosphinobenzaldimino (P^N) ligand). All compounds were fully characterized using spectroscopic and analytical techniques, including ¹H, ¹³C, and ³¹P NMR and IR spectroscopies, mass spectrometry and elemental analysis. Selected neutral palladium complexes were evaluated as catalyst precursors in ethylene oligomerisation reactions, after activation with a co-catalyst (MMAO, EtAlCl₂, or Et₂AlCl).     

Synthesis of short straight-chain alkylamine based hyperbranched nickel complexes and their catalytic performance of ethylene oligomerization

Short straight-chain alkylamine based hyperbranched molecules and their corresponding salicylaldimine nickel complexes have been synthesized in high yield and characterized by FTIR, ¹H-NMR and mass spectrometry. The optimal reaction parameters were determined under the catalytic system of methylaluminoxane (MAO) as co-catalyst and toluene as solvent. Under these conditions, the effect of catalyst structure, solvent and co-catalyst were determined. Upon activation of MAO in toluene, ethylene oligomerization products were homogeneous distribution of butene, hexene and octene with trace higher olefin. The same catalytic system under cyclohexane and methyl cyclohexane as solvent, however, produced majority of butene. Under the activation of EtAlCl₂, Et₂AlCl and EASC as co-catalyst in toluene, ethylene oligomerization reaction was tandem with Friedel-Crafts reaction in catalytic system.     

Polymerization of Cyclohexene Oxide By Organoaluminum Compounds

Abstract

The polymerization of cyclohexene oxide (CHO) by various organoaluminum compounds such as R₃Al (R = Me, Et, i-Bu), Et₂AlCl, and EtAlCl₂ is reported. Ethyl-substituted aluminum compounds were found to be very effective for this polymerization. As more chlorine atom is substituted on the aluminum atom, the polymer yield was increased though the molecular weight was decreased. The polymer yields at varying monomer-to-catalyst mole ratios (M/C) were similar (80–93%). The temperature and solvent effect for the present polymerization were also studied. The present poly(CHO) was a less stereoregular (atactic) isomer, regardless of catalysts and polymerization conditions. The resulting poly(CHO) was a white powder ad was soluble in aromatic and halogenated hydrocarbon solvents such as benzene, chlorobenzene, CCl₄, chloroform, etc.     

Carbon-13 NMR spectroscopy of acrylic monomer and Lewis acid complexes

¹³C NMR spectra of acrylic monomers complexed with a Lewis acid were measured and their electronic structures discussed in relation to their alternating copolymerizability. The β-carbon of acrylonitrile and methacrylonitrile showed a downfield shift due to the complex formation with the Lewis acid, while the α-carbon showed an upfield shift and the nitrile carbon showed no significant shift. The degree of shift of olefinic carbons decreased in the following order: AlCl₃ > EtAlCl₂ > Et_1.5AlCl_1.5 > Et₂AlCl > SnCl₄, EtOAlCl₂ > Et(EtO)AlCl, which seems to run parallel to the Lewis acidity and acid strength. On the other hand, the chemical shift of olefinic carbons of methyl acrylate, methyl methacrylate, and olefinic diesters was influenced little by complex formation with Lewis acids, whereas the carbonyl and alkoxyl carbons were deshielded significantly by the complex formation. These results are discussed in terms of electron distribution on the carbons and an alternating polymerization mechanism.     

A chiral auxiliary derived from levoglucosenone in asymmetric Diels-Alder transformations

The Diels-Alder reaction of the acrylate derived from levoglucosenone with cyclopentadiene was studied under several conditions, in the presence and absence of a Lewis acid. The results showed satisfactory diastereomeric excess and the ratio of cycloadducts was found to depend on the reaction conditions. A reversal in stereoselectivity was observed when EtAlCl₂ or Et₂AlCl were employed as Lewis acids.     

The first one-pot synthesis of alkoxycyclopropanes via cyclometalation of styrene with ClnAlEt3−n and RCO2R′ mediated by Cp2ZrCl2

The one-pot cyclopropanation of styrene using Cl_nAlEt_3−n (Et₂AlCl, EtAlCl₂, AlCl₃) and carboxylic esters in the presence of Cp₂ZrCl₂ as catalyst gives rise to alkoxycyclopropanes.     

Dichlorovanadium (IV) complexes with salen‐type ligands for ethylene polymerization

Vanadium complexes with tetradentate salen‐type ligands were first time explored in ethylene polymerizations. The effects of the vanadium complex structure, the alkyl aluminum cocatalysts type (EtAlCl₂, Et₂AlCl, Et₃Al, and MAO), and the polymerization conditions (Al/V molar ratio, temperature) on polyethylene yield were explored. It was found that EtAlCl₂ in conjunction with investigated vanadium complexes produced the most efficient catalytic systems. It was shown, moreover, that the structural changes of the tetradentate salen ligand (type of bridge which bond donor nitrogen atoms and type of substituent on aryl rings) affected activity of the catalytic system. The complexes containing ligands with cyclohexylene bridges were more active than those with ethylene bridges. Furthermore, the presence of electron‐withdrawing groups at the para position and electron‐donating substituents at the ortho position on the aryl rings of the ligands resulted in improved activity in relation to the systems with no substituents (with the exception of bulky t‐Bu group). The results presented also revealed that all vanadium complexes activated by common organoaluminum compounds gave linear polyethylenes with high melting points (134.8–137.6 °C), high molecular weights, and broad molecular weight distribution. The polymer produced in the presence of MAO possesses clearly lower melting point (131.4 °C) and some side groups (around 9/1000 C). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6940–6949, 2008     

Acylation of N-p-toluenesulfonylpyrrole under Friedel-Crafts conditions: evidence for organoaluminum intermediates

The Friedel-Crafts acylation of N-p-toluenesulfonylpyrrole under Friedel-Crafts conditions has been reinvestigated. Evidence is presented in support of the hypothesis that when AlCl₃ is used as the Lewis acid, acylation proceeds via reaction of an organoaluminum intermediate with the acyl halide. This leads to the production of the 3-acyl derivative as the major product. With weaker Lewis acids (EtAlCl₂, Et₂AlCl) or less than 1 equiv of AlCl₃ the relative amount of 2-acyl product is increased. A mechanistic rationalization is presented to explain these data.     

Alternating copolymerization of 1- and 2-vinylnaphthalene with methyl methacrylate by using diethylaluminum chloride

The alternating copolymerization of 1- and 2-vinylnaphthalene (1-VNap and 2-VNap) with methyl methacrylate (MMA) by using diethylaluminum chloride (Et₂AlCl) in toluene at 0°C has been studied. No polymerization could occur without Et₂AlCl, and alternating copolymers were obtained only when an equimolar amount of Et₂AlCl with MMA was supplied. Through ¹H-NMR analyses on both dyad and triad of alternating deuterated 1- and 2-α-d-VNap–MMA copolymers, each configuration could be described successfully by a single parameter, coisotacticity σ, whose value was estimated as 0.41 for the former and 0.56 for the latter copolymer, respectively. A rather low coisotacticity of copoly(1-VNap–MMA) was explained in the terms of steric effect (peri effect) of 1-VNap monomer.     

Olefin polymerization behavior of titanium(IV) alkoxo complexes with fluorinated diolate ligands: The impact of the chelate ring size and the nature of organoaluminum compounds

Titanium(IV) coordination compounds are effectively used as precatalysts for ethylene polymerization and copolymerization with other olefins. New titanium(IV) complexes 3b – d with ligands containing two diphenylcarbinol fragments linked by the perfluorinated hydrocarbon units –CF₂– or –C₂F₄– were synthesized. The structures of complexes 3b and 3d were determined by X-ray diffraction. Titanium atoms in 3b have a distorted trigonal-bipyramidal coordination environment while spiro-complex 3d is characterized by tetrahedral molecular geometry. The catalytic behavior of complexes activated by mixtures of Bu₂Mg and alkylaluminium chlorides from among Me₂AlCl, Et₂AlCl, EtAlCl₂, and Et₃Al₂Cl₃ were studied. The resulting catalytic systems catalyze ethylene polymerization to afford ultra-high molecular weight polyethylene, suitable for modern processing methods, and the solvent-free solid state formation of super high-strength (1.37–2.75 GPa) and high-modulus (up to 138 GPa) oriented film tapes. The same catalytic systems catalyze ethylene copolymerization with 1-hexene to afford high molecular weight semicrystalline elastomeric polymers containing up to 20% of comonomer units.     

Alternating copolymerization of styrene and methyl α-chloroacrylate with diethylaluminum chloride

The alternating copolymerization of styrene and methyl α-chloroacrylate (MCA) with diethylaluminum chloride (Et₂AlCl) in benzene at 0°C has been investigated. The copolymer has an equimolar composition irrespective of the feed monomer composition, the copolymer yield and the amount of Et₂AlCl used. The copolymerization proceeds first very rapidly and then rather slowly after attaining a certain yield which varies proportionally to the amount of Et₂AlCl used. A maximum copolymer yield is observed at about 60% MCA feed composition. The ¹H-NMR analyses of dyad, triad, and pentad of the alternating deuterated α-d-St-MCA copolymer indicate that the configuration of this copolymer can be explained by a single parameter, coisotacticity σ(σ = 0.69). A favorable mechanism of the alternating propagation as well as of the stereoregularity control is discussed.     

Ene reaction of Diels–Alder adducts of levoglucosenone and 1,3-dienes with acetaldehyde

Diels–Alder adducts of levoglucosenone with isoprene, butadiene and piperylene in the presence of AlCl₃ smoothly react with acetaldehyde or benzaldehyde to give products of the ene reaction, the hydroxy group of the primary intermediates participating in the formation of semiketal moiety. The yields of the reaction products depend both on the Lewis acid used (AlCl , BF ·Et O, ZnBr , SnCl or EtAlCl₂) and on the nature of the substrate.     

Hydrogenation of β-Keto Sulfones to β-Hydroxy Sulfones with Alkyl Aluminum Compounds: Structure of Intermediate Hydroalumination Products

β-Hydroxy sulfones are important in organic synthesis. The simplest method of β-hydroxy sulfones synthesis is the hydrogenation of β-keto sulfones. Herein, we report the reducing properties of alkyl aluminum compounds R₃Al (R = Et, i-Bu, n-Bu, t-Bu and n-Hex); i-Bu₂AlH; Et₂AlCl and EtAlCl₂ in the hydrogenation of β-keto sulfones. The compounds i-Bu₂AlH, i-Bu₃Al and Et₃Al are the at best reducing agents of β-keto sulfones to β-hydroxy sulfones. In reactions of β-keto sulfones with aluminum trialkyls, hydroalumination products with β-hydroxy sulfone ligands [R₂AlOC(C₆H₅)CH₂S(O)₂(p-R¹C₆H₄]_n [where n = 1,2; 2aa: R = i-Bu, R¹ = CH₃; 2ab: R = i-Bu, R¹ = Cl; 2ba: R = Et, R¹ = CH₃; 2bb: R = Et, R¹ = Cl] and {[Et₂AlOC(C₆H₅)CH₂S(O)₂(p-ClC₆H₄]∙Et₃Al}_n 3bb were obtained. These complexes in the solid state have a dimeric structure, while in solutions, they appear as equilibrium monomer–dimer mixtures. The hydrolysis of both the isolated 2aa, 2ab, 2ba, 2bb and 3bb and the postreaction mixtures quantitatively leads to pure racemic β-hydroxy sulfones. Hydroalumination reaction of β-keto sulfones with alkyl aluminum compounds and subsequent hydrolysis of the complexes is a simple and very efficient method of β-hydroxy sulfones synthesis.