CIDNP study of the Ni(acac)2-catalyzed reaction of triethylaluminum with chloroform

CIDNP effects were found in the Ni(acac)₂-catalyzed reaction of Et₃Al with CHCl₃. The effects appear in the products of transformation of the diffusion radical pair of the ethyl and dichloromethyl radicals. The radical route is a side process in this reaction, and the main products, Et₂AlCl, ethane, and ethylene, are formed by a nonradical route. A general mechanism of the reactions of Et₃Al with CHCl₃ and CCl₄ including radical and ioncoordination processes was suggested. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1003–1006, May, 1999.     

Photoinitiated oxidation of NADH catalyzed by horseradish peroxidase studied by chemically induced dynamic nuclear polarization

The photoinitiated oxidation of β-NADH catalyzed by horseradish peroxidase (Per³⁺) was studied by time-resolved photoinitiated chemically induced dynamic nuclear polarization (CIDNP). The polarization observed on protons at the C(4) atom of the β-NADH molecule is evidence for the reversible one-electron transfer between the radical cation NADH^+· and the ferroperoxidase intermediate (Per²⁺). A new approach based on electron transitions in the (NADH^+· Per²⁺) pair was proposed to describe the formation of CIDNP effects in systems including quartet (Q)—doublet (D) electron transitions. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1090–1094, July, 2006.     

(η5-C5H5)2TiCl2- hydroalumination of α-olefins with Et3Alhydroalumination of α-olefins with Et3Al

A preparative method for the synthesis of (alkyl)diethylalanes from α-olefins and Et₃Al catalyzed by Cp₂TiCl₂ (Cp=η⁵-C₅H₅)is proposed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 712–715, April, 1998.     

Chemically induced dynamic nuclei polarization and free radicals in the reaction of triethylaluminum with nitrobenzene

The reaction of triethylaluminum with nitrobenzene in hydrocarbon solvents was studied by GC-MS and CIDNP techniques. Radical intermediates participating in a complex process of reduction and alkylation of nitrobenzene were observed in the reaction products (nitrobenzene radical anion, ethyl radical, and nitroxyl radical), and routes of their formation and decay were discussed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1979–1982, October, 1998.     

Addition of CCl4 to unsaturated compounds catalyzed by M3(CO)12 (M=Fe, Ru, Os)

The addition of CCl₄ to hex-1-ene and to the methyl ester ofN-(trans-cinnamoyl)-l-proline (2) catalyzed by M₃(CO)₁₂ or by the M₃(CO)₁₂+DMF system (M=Fe, Ru, Os) was studied. The use of ruthenium and osmium dodecacarbonyls in combination with DMF increases the yields of adducts CCl₃CH₂CHClC₄H₉ (4) and PhCHClCH(CCl₃)C(O)R′ (3) over those obtained in reactions catalyzed by the same carbonyls without DMF. In addition to adduct3, salts [M(CO₃)Cl₃]⁻[Me₂NH₂]⁺ were isolated from the products of the reaction between CCl₄ and1 in the presence of M₃(CO)₁₂+DMF (M=Ru, Os). These salts do not catalyze this reaction and apparently result from chain termination. Experimental results in favor of a coordination mechanism of the addition of CCl₄ to olefins in the presence of Ru₃(CO)₁₂ and Os₃(CO)₁₂ were obtained. Translated fromIzvestiya Akademii Nauk Seriya Khimicheskaya, No. 6, pp. 1174–1179, June, 1997.     

Synthesis and transformation of metallacycles. 25. On a mechanism of the Ni(acac)2-catalyzed conversion of 3-alkyl-1-ethylalumacyclopentanes into 1,1-disubstituted cyclopropanes

The reactions of 3-alkyl-1-ethylalumacyclopentanes with allyl halides in the presence of Ni(acac)₂ as a catalyst were studied by dynamic NMR spectroscopy. Under the action of Ni complexes, alumacyclopentanes initially undergo intramolecular hydride transfer to give but-3-enyl(ethyl)aluminum hydrides and then react with the starting allyl halide, yielding but-3-enyl(ethyl)aluminum halides. Subsequent intramolecular carboalumination affords the corresponding 1,1-disubstituted cyclopropanes.     

Mechanism of hydrolysis of azalactones catalyzed by a complex of Cu(II) with (S)-2-[(N-benzylpropyl)amino]benzaldoxime

The hydrolysis of 2-methyl-4-benzyl-5(4H)oxazolone (MBA) in a mixture of water and MeCN has been studied — both the spontaneous reaction and that catalyzed by a complex of Cu(II) with (S)-2-[(N-benzylpropyl)amino]benzaldoxime (1). It has been shown that the complex 1 is an effective catalyst for the hydrolysis of MBA (chymotrypsin does not catalyze MBA hydrolysis). The mechanism of MBA hydrolysis catalyzed by this complex includes the formation of a mixed catalyst—substrate complex in which the MBA is coordinated with the metal ion through the N ³ atom. It is suggested that the oxygen atom of the ionized oxime group in such a complex attacks the imine C ² atom of the MBA intramolecularly; this is the rate-determining stage. The change in the order of hydrolysis with respect to the catalyst from 1 to 1/2 when the concentration of 1 is increased indicates that the complex catalyst exists in aqueous solution in two forms, dimeric and monomeric, which are in equilibrium, and only the monomeric form of the complex is responsible for the catalysis. With an excess of the substrate we observe inhibition of the MBA hydrolysis — possibly an indirect indication of participation in the transition state by a water molecule coordinated in an apical position of the complex, which is displaced by excess substrate.A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, Moscow 117813. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 536–546, March, 1992.     

Oxidation of alkanes and alcohols with hydrogen peroxide catalyzed by complex Os3(CO)10(µ‐H)2

Trinuclear carbonyl hydride cluster, Os₃(CO)₁₀(µ‐H)₂, catalyzes oxidation of cyclooctane to cyclooctyl hydroperoxide by hydrogen peroxide in acetonitrile solution. The hydroperoxide partly decomposes in the course of the reaction to afford cyclooctanone and cyclooctanol. Selectivity parameters obtained in oxidations of various linear and branched alkanes as well as kinetic features of the reaction indicated that the alkane oxidation occurs with the participation of hydroxyl radicals. A similar mechanism operates in transformation of benzene into phenol and styrene into benzaldehyde. The system also oxidizes 1‐phenylethanol to acetophenone. The kinetic study led to a conclusion that oxidation of alcohols does not involve hydroxyl radicals as main oxidizing species and apparently proceeds with the participation of osmyl species, ‘Os?O’. Copyright © 2010 John Wiley & Sons, Ltd.     

Copolymerization of norbornene and 5‐norbornene‐2‐yl acetate using novel bis(β‐ketonaphthylamino)Ni(II)/B(C6F5)3/AlEt3 catalytic system

Vinyl‐type copolymerization of norbornene (NBE) and 5‐NBE‐2‐yl‐acetate (NBE‐OCOMe) in toluene were investigated using a novel homogeneous catalyst system based on bis(β‐ketonaphthylamino)Ni(II)/B(C₆F₅)₃/AlEt₃. The copolymerization behavior as well as the copolymerization conditions, such as the levels of B(C₆F₅)₃ and AlEt₃, temperature, and monomer feed ratios, which influence on the copolymerization were examined. Without combination of AlEt₃, the catalytic bis(β‐ketonaphthylamino)Ni(II)/B(C₆F₅)₃ exhibited very high catalyst activity for polymerization of NBE. Combination of AlEt₃ in catalyst system resulted in low conversion for polymerization of NBE. For copolymerization of NBE and NBE‐OCOMe, involvement of AlEt₃ in catalyst is necessary. Slight addition of NBE‐OCOMe in copolymerization of NBE and NBE‐OCOMe gives rise to significant increase of catalyst activity for catalytic system bis(β‐ketonaphthylamino)Ni(II)/B(C₆F₅)₃/AlEt₃. Nevertheless, excess increase of the NBE‐OCOMe content in the comonomer feed ratios results in decrease of conversion as well as activity of catalyst. The achieved copolymers were confirmed to be vinyl‐addition copolymers through the analysis of FTIR, ¹H NMR, and ¹³C NMR spectra. ¹³C NMR studies further revealed the composition of the copolymer and the incorporation rate was 7.6–54.1 mol % ester units at a content of 30–90 mol % of the NBE‐OCOMe in the monomer feeds ratios. TGA analysis results showed that the copolymer exhibited good thermal stability (T_d > 410 °C) and failed to observe the glass transitions temperature over 300 °C. The copolymers are confirmed to be noncrystalline by WAXD analysis results and show good solubility in common organic solvents. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3990–4000, 2009     

4'-(3-甲氧基-4-羟基苯基)-2,2':6', 2"-三联吡啶及其铜、锌配合物的合成、结构和性质

通过一锅反应制备了4′-(3-甲氧基-4-羟基苯基)-2,2′∶6′,2″-三联吡啶(L),通过重结晶的方法得到了其醋酸盐单晶体(HL)(CH3COO)(1),并以L为配体组装了过渡金属配合物[Cu(NO3)(CH3OH)L](NO3)(2)和[Zn(NO3)2L](C2H5OH)(3),通过元素分析、IR光谱和单晶X-射线衍射等表征了3个化合物的结构。结果表明,化合物1中,三联吡啶环呈反-反构型,而在2和3中,三联吡啶环呈现出顺-顺构型,然后采取三齿螯合模式连接金属离子形成单核单元。3个化合物中,三联吡啶分子之间以及它们与溶剂分子之间形成的氢键、π-π堆积和范德华力等相互作用将化合物1~3的单核单元连接形成三维网状结构。     

Chemically induced dynamic nuclear polarization and the mechanism of the reaction of Et<Subscript>3</Subscript>Al with CCl<Subscript>4</Subscript> in the presence of transition metal complexes

Integral effects of chemically induced ¹H and ¹³C nuclear polarization are reported for the reaction of Et₃Al with CCl₄ catalyzed by Pd(acac)₂, Cu(acac)₂, and Cp₂TiCl₂; for the reaction of (n-C₈H₁₇)₃Al with CCl₄ in the absence of a catalyst and in the presence of Ni(acac)₂; and for the reaction of the cyclic organoaluminum compound 1-ethyl-3-butylaluminacyclopentane with CCl₄ in the presence of Pd(acac)₂. A scheme of the catalytic cycle of this reaction predicting the formation of both radical and nonradical products is derived from the observed chemically induced dynamic nuclear polarization (CIDNP) effects and from data on the products of the reaction between Et₃Al and CCl₄ in the presence of Pd(acac)₂. According to the results of qualitative analysis of the CIDNP effects, the reactions of the trialkylalanes and the cyclic organoaluminum compound with CCl₄ in the presence of various metal complexes proceeded via similar mechanisms.     

Acid-catalyzed attack of the dinitrogen ligand in thecis-(Me2PhP)4Mo(N2)2 andtrans-(Ph2PCH2CH2PPh2W(N2)2 complexes by nitronium and nitrosonium cations with the formation of nitrogen oxides

The interaction of labeled dinitrogen complexescis-(Me₂PhP)₄Mo(¹⁵N₂)₂ andtrans-(dppe)₂W(¹⁵N₂)₂ with non-labeled nitronium and nitrosonium fluoroborates,¹⁴NO₂BF₄ and¹⁴NOBF₄, in sulfolane at room temperature in the presence of H₂SO₄ results in rapid formation of labeled nitrous and nitric oxides (¹⁵N¹⁴NO,¹⁵NO), as well as¹⁵N¹⁴N. The yield of the products depends on the reagent ratio and reaches 10–20 mol. % per mole of a complex under optimum conditions. The mechanism of the reactions found is proposed. It involves the step of protonation of the dinitrogen ligand to form the corresponding hydrazido(2–) derivatives, which are then attacked by nitronium or nitrosonium cations. In accordance with the mechanism proposed, it was established that the hydrazido(2–) complexes, (Me₂PhP)₃Mo(¹⁵N₂H₂)Cl₂ and (dppe)₂W(¹⁵N₂H₂)Cl₂, are capable of forming¹⁵N¹⁴NO,¹⁵NO, and¹⁵N¹⁴N under the action of¹⁴NO₂BF₄ and¹⁴NOBF₄ in the absence of an acid.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 13–13, July, 1995.     

Synthesis, thermal, spectral and magnetic studies of complexes of Co(II), Ni(II), Cu(II), Ru(II), Pd(II) and Pt(II) with 2, 3-disubstituted quinazolin-(3H)-4-ones

A number of complexes of Co(II), Ni(II), Cu(II), Ru(II), Pd(II) and Pt(II) with 2-methyl-3-(carboxy methyl) quinazolin (3H)-4-one (MCMQ) and 2-phenyl-3-(carboxy methyl) quinazolin (3H)-4-one (PCMQ) have been synthesized and characterized by analytical, conductivity, thermal, magnetic, infrared, electronic, proton magnetic resonance and electron spin resonance spectral data. Based on analytical data, the stoichiometry and the association with other molecules of the complexes have been determined. Conductivity data show that all these complexes are nonelectrolytes. Infrared and PMR spectral data indicate that both the ligands are uninegative bidentate with all the metal ions. Based on electronic spectral data, the geometries of the complexes have been indicated. Electronic spectral parameters for Co(II) and Ni(II) and ESR parameters for Cu(II) complexes have been calculated and relevant conclusions have been drawn with respect to the nature of bonds present in them.     

Copolymerization of norbornene with methoxycarbonylnorbornene catalyzed by Ni{CF3C(O)CHC[N(naphthyl)]CH3}2/B(C6F5)3 catalytic system and good processability for Dry/Wet phase inversion and electrospinning technique

Copolymerization of norbornene (NB) with methoxycarbonylnorbornene (NB‐COOCH₃) was carried out with catalytic system of Ni{CF₃C(O)CHC[N(naphthyl)]CH₃}₂ and B(C₆F₅)₃ in toluene. The catalytic system exhibited higher activity 2.69 × 10⁵ (gpolymer/mol Ni h) for copolymerization of norbornene and methoxycarbonylnorbornene. The influence results of the comonomer feed content on the polymerization showed that the NB‐COOCH₃ has a very high insertion ratio in all copolymers, and the NB‐COOCH₃ content in copolymers can be controlled to be 7.9–77.6 mol % at content of 10–90 mol % of the NB‐COOCH₃ in the monomer feeds ratios. The reactivity ratios, r_NB‐COOCH3 = 0.578 and r_NB = 0.859, were determined by the Kelen–TÜdÕs method. Copolymers were processed by solution casting method, dry/wet phase inversion technique, and electrospinning. The films prepared by solution casting method showed good transparency in the visible region. The membranes processed by dry/wet phase inversion technique were microporous structures. The fibers diameters fabricated by electrospinning were about 3 μm. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Ni(II) and Pd(II) complexes bearing novel bis(β‐ketoamino) ligand and their catalytic activity toward copolymerization of norbornene and 5‐norbornene‐2‐yl acetate combined with B(C6F5)3

Two complexes Mt{C₁₀H₈(O)C[N(C₆H₅)]CH₃}₂ [Mt = Ni(II); Mt = Pd(II)] were synthesized, and the solid‐state structures of the complexes have been determined by single‐crystal X‐ray diffractions. Homopolymerization of norbornene (NB) and copolymerization of NB and 5‐norbornene‐2‐yl acetate (NB‐OCOCH₃) were carried out in toluene with both the two complexes mentioned above in combination with B(C₆F₅)₃. Both the catalytic systems exhibited high activity toward the homopolymerization of NB (as high as 2.7 × 10⁵ g_polymer/mol_Ni h, for Ni(II)/B(C₆F₅)₃ and 2.1 × 10⁵ g_polymer/mol_Pd h for Pd(II)/B(C₆F₅)₃, respectively.). Although the Pd(II)/B(C₆F₅)₃ shows very lower activity toward the copolymerization of NB with NB‐OCOCH₃, Ni(II)/B(C₆F₅)₃ shows a high activity and produces the addition‐type copolymer with relatively high molecular weights (MWs; 1.80–2.79 × 10⁵ g/mol) as well as narrow MW distribution (1.89–2.30). The NB‐OCOCH₃ content in the copolymers can be controlled up to 5.8–12.0% by varying the comonomer feed ratios from 10 to 50%. The copolymers exhibited high transparency, high glass transition temperature (T_g > 263.9 °C), better solubility, and mechanical properties compared with the homopolymer of NB. The reactivity ratios of the two monomers were determined to be r_NB‐OCOMe = 0.08, r_NB = 7.94 for Ni(II)/B(C₆F₅)₃ system, and r_NB‐OCOMe = 0.07, r_NB = 6.49, for Pd(II)/B(C₆F₅)₃ system by the Kelen‐Tüdõs method. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

C–C bridged Ni(II) complexes bearing β‐keto‐9‐fluorenyliminato ligands prepared by different in situ bonding mechanisms and their use in catalytic (co)polymerization of norbornene and styrene

Two C–C bridged Ni(II) complexes bearing β‐keto‐9‐fluorenyliminato ligands with electron‐withdrawing groups (─CF₃), Ni{PhC(O)CHC[N(9‐fluorenyl)]CF₂}₂ (Ni 1 ) and Ni{CF₃C(O)CHC[N(9‐fluorenyl)]Ph}₂ (Ni 2 ), were synthesized by metal coordination reaction and different in situ bonding mechanisms. The C–C bridged bonds of Ni 1 were formed by in situ intramolecular trifluoromethyl and 9‐fluorenyl carbon–carbon cross‐coupling reaction and those of Ni 2 were formed by in situ intramolecular 9‐fluorenyl carbon–carbon radical coupling reaction mechanism. The obtained complexes were characterized using ¹H NMR spectroscopy and elemental analyses. The crystal and molecular structures of Ni 1 and Ni 2 with C–C bridged configuration were determined using X‐ray diffraction. Ni 1 and Ni 2 were used as catalysts for norbornene (NB) polymerization after activation with B(C₆F₅)₃ and the catalytic activities reached 10⁶ g_polymer mol_Ni^?1 h^?1. The copolymerization of NB and styrene catalyzed by the Ni 1 /B(C₆F₅)₃ system showed high activity (10⁵ g_polymer mol_Ni^?1 h^?1) and the catalytic activities decreased with increasing feed content of styrene. All vinyl‐type copolymers exhibited high molecular weight (10⁴ g mol^?1), narrow molecular weight distribution (M_w/M_n = 1.71–2.80), high styrene insertion ratios (11.13–50.81%) and high thermal stability (T_d > 380°C) and could be made into thin films with high transparency in the visible region (400–800 nm).     

Synthesis,crystal structures and luminescence properties of seven mononuclear zinc(II), cadmium(II), cobalt(II) and nickel(II) complexes with 5‐(4‐methylphenyl)‐3‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazole

Due to their versatile coordination modes and metal‐binding conformations, triazolyl ligands can provide a wide range of possibilities for the construction of supramolecular structures. Seven mononuclear transition metal complexes with different structural forms, namely aquabis[3‐(4‐methylphenyl)‐5‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazolato‐κ²N ¹,N ⁵]zinc(II), [Zn(C₁₄H₁₁N₄)₂(H₂O)], (I), bis[5‐(4‐methylphenyl)‐3‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazole‐κ²N ³,N ⁴]bis(nitrato‐κO )zinc(II), [Zn(NO₃)₂(C₁₄H₁₂N₄)₂], (II), bis(methanol‐κO )bis[3‐(4‐methylphenyl)‐5‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazolato‐κ²N ¹,N ⁵]zinc(II), [Zn(C₁₄H₁₁N₄)₂(CH₄O)₂], (III), diiodidobis[5‐(4‐methylphenyl)‐3‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazole‐κ²N ³,N ⁴]cadmium(II), [CdI₂(C₁₄H₁₂N₄)₂], (IV), bis[5‐(4‐methylphenyl)‐3‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazole‐κ²N ³,N ⁴]bis(nitrato‐κO )cadmium(II), [Cd(NO₃)₂(C₁₄H₁₂N₄)₂], (V), aquabis[3‐(4‐methylphenyl)‐5‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazolato‐κ²N ¹,N ⁵]cobalt(II), [Co(C₁₄H₁₁N₄)₂(H₂O)], (VI), and diaquabis[3‐(4‐methylphenyl)‐5‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazolato‐κ²N ¹,N ⁵]nickel(II), [Ni(C₁₄H₁₁N₄)₂(H₂O)₂], (VII), have been prepared by the reaction of transition metal salts (Zn^II, Cd^II, Co^II and Ni^II) with 3‐(4‐methylphenyl)‐5‐(pyridin‐2‐yl)‐1H‐1,2,4‐triazole (pymphtzH) under either ambient or hydrothermal conditions. These compounds have been characterized by elemental analysis, IR spectroscopy and single‐crystal X‐ray diffraction. All the complexes form three‐dimensional supramolecular structures through hydrogen bonds or through π–π stacking interactions between the centroids of the pyridyl or arene rings. The pymphtzH and pymphtz⁻ entities act as bidentate coordinating ligands in each structure. Moreover, all the pyridyl N atoms are coordinated to metal atoms (Zn, Cd, Co or Ni). The N atom in the 4‐position of the triazole group is coordinated to the Zn and Cd atoms in the crystal structures of (II), (IV) and (V), while the N atom in the 1‐position of the triazolate group is coordinated to the Zn, Co and Ni atoms in (I), (III), (VI) and (VII).     

Synthesis and electrochemical study of 3- and 4-(2-pyridyl)-1,3-benzothiazole complexes with transition metals (CoII, NiII, and CuII). Molecular structure of bis{(4-(2-pyridyl)-1,3-benzothiazole)copper(ii)} tetraacetate

A series of the M(L)Cl₂ · nH₂O and {M(L)}₂(OAc)₄ complexes (M = Ni^II, Co^II, and Cu^II; L is 3- and 4-(2-pyridyl)-1,3-benzothiazole) were synthesized by the reaction of L with MX₂ · nH₂O (X = Cl, OAc) in ethanol. The molecular and crystal structures of the CuL₂(OAc)₄ binuclear complex (L is 4-(2-pyridyl)benzothiazole) were determined by X-ray diffraction analysis. The copper atoms have a distorted tetragonal bipyramidal environment and are coordinated to the nitrogen atom of the pyridine moiety of the ligand and to two oxygen atoms of the bridging acetate ligands. The Cu-Cu distance is 2.6129(9) Å. The electrochemical behavior of the synthesized ligands and complexes was studied using the cyclic voltammetry and rotating disk electrode techniques in DMF solutions (0.1 M Bu₄NClO₄). The primary reduction of all the complexes under study is directed to the metal.