Catalytic Copolymerization of Ethene and Carbon Monoxide on Nickel Complexes

Can palladium be replaced by nickel? For the industrial copolymerization of carbon monoxide and ethene a palladium catalyst is used which cannot be recovered—a cheaper procedure would be desirable. The presented complex 1 is the first structurally characterized nickel compound which does not polymerize ethene but a mixture from carbon monoxide and ethene unter mild conditions to give a perfectly alternating polyketone.     

NaA分子筛膜催化剂上CO和C2H4混合气的选择性氧化反应

Defect-free zeolite NaA membranes were coated onto the surface of spherical Pt/Al2O3 particles using a two-step hydrothermal method. The structure and morphology of the synthesized composite catalysts were characterized using XRD and SEM techniques, respectively. The results indicated a layer of compact and uniform NaA molecular sieve membrane with a thickness of about 20 滋m was coated on the spherical Pt/Al2O3 particles after the two-step hydrothermal synthesis. The prepared NaA membrane coated catalysts were used in the oxidation of a mixture of CO and C2H4 to study the reactant selectivity over the coated zeolite NaA membranes. Under the optimized conditions, the oxidation selectivity for CO over C2H4 on the composite catalyst was as high as 96%. The feasible application of this composite membrane coated catalyst to the selective removal of CO in the presence of C2H4 was anticipated.     

一氧化碳与烯烃共聚及其功能高分子

本文综述了一氧化碳与烯烃共聚合成聚酮的方法，共聚反应机理以及聚酮在合成其他功能高分子方面的应用。     

New Catalyst for the Copolymerization of Styrene with Carbon Monoxide

Carbonmonoxide(CO)witholefinscanbec0p0lymerizedwithfreeradicalinitiatorsorn0bletransitionmetalc0mpoundcatalystS.Thefreeradicalinitiatedcopolymerizationunderhighgaspressure(upt0l(X)Mpa)andl2O-l65oC',whereasthemostusednobletransitionmetalcompoundsf0rthec0polymerizati0nofcarbonmonoxidewitholefinsarepalladiumorrhodiumcompounds"'.In0urw0rk,theneodymiumcomp0undcatalystsystemswerefoundt0beactiveforthecopolymerizationofstyreneandcarbonm0noxide.Thecopolymerizationofstyreneandcarbonm0n0xidewascAned0u…     

Synthesis,Characterization, and X‐ray Crystal Structures of (Diphosphine)Ni(dmit) and (Diphosphine)Ni(dmio) (Diphosphine = dppv,dppb) Complexes

Four complexes with the ligands dmit and dmio were synthesized. Reaction of (PhCO)₂(dmit) and (PhCO)₂(dmio) with MeONa afforded the intermediates 2‐thioxo‐1,3‐dithiole‐4,5‐dithiolate dianion and 2‐oxo‐1,3‐dithiole‐4,5‐dithiolate dianion, respectively. Reaction of the two dianions with (diphosphine)NiCl₂ [diphosphine = (Z)‐1, 2‐bis(diphenylphosphanyl)ethane (dppv), 1,2‐bis(diphenylphosphanyl)benzene (dppb)] gave (dppv)Ni(dmit) ( 1 ), (dppb)Ni(dmit) ( 2 ), (dppv)Ni(dmio) ( 3 ), and (dppb)Ni(dmio) ( 4 ). This synthesis route was found to be an efficient pathway to prepare dmit and dmio ligand complexes. Complexes, 1 – 4 were fully characterized by elemental analysis and IR, ¹H NMR, ¹³C NMR, and ³¹P NMR spectroscopy. In addition, the molecular structures of 1 , 3 and 4 were established by X‐ray diffraction.     

Palladium Aryl Sulfonate Phosphine Catalysts for the Copolymerization of Acrylates with Ethene

The reaction of 2‐[bis(2‐methoxy‐phenyl)phosphanyl]‐4‐methyl‐benzenesulfonic acid (a) and 2‐[bis(2′,6′‐dimethoxybiphenyl‐2‐yl)phosphanyl]benzenesulfonic acid (b) with dimethyl(N,N,N′,N′‐tetramethylethylenediamine)‐palladium(II) (PdMe₂(TMEDA)) leads to the formation of TMEDA bridged palladium based polymerization catalysts ( 1a and 1b ). Upon reaction with pyridine, two mononuclear catalysts are formed ( 2a and 2b ). These catalysts are able to homopolymerize ethylene and also copolymerize ethylene with acrylates or with norbornenes. With ligand b , high molecular weight polymers are formed in high yields, but higher comonomer incorporations are obtained with ligand a .

     

Characterization and Activity of Iron-Manganese Catalysts for Carbon Monoxide Hydrogenation

Studies on the structural changes and catalytic behavior of iron-manganese catalysts for CO hydrogenation were conducted using Mossbauer spectroscopy, X-ray diffraction, temperature programmed reduction and kinetic measurements. It was observed that the reduction of the mixed oxide catalyst precursors proceeds via the formation of Fe_3-xMn_xO₄,Mn_3-xFe_xO₄ mixed spinel and Fe_1-zMn₂O mixed oxide to α-iron and MnO. After use for CO hydrogenation, catalysts are oxidized as well as carburized. The Mn_3-yFe_yO₄ mixed spinel and Fe_1-2Mn_zO mixed oxide are the most powerful phases for olefin production. The highest attainable 2–4 low carbon olefin selectivity is 41% with an 86% conversion level. Higher manganese content or lower reduction temperatures may change the carbide formed from χ-Fe₅C₂ to the more unstable ?′-Fe₂₂C. Carbide formation is greatly dependent on manganese content and activation procedure used.     

Hydrogen and Carbon Monoxide at Terra Nova Bay (ANTARCTICA)

Abstract

Studies on atrazine ozonation performed in methanol containing solutions showed a strong influence of the methanol content which might favour direct O₃ reactions as compared to processes induced by OH radicals. The importance of the slackening effect on the degradation rate of atrazine (which demonstrates a scavenger activity) was evaluated in various solvent compositions and pseudo-kinetic constants k' were found to be in the 10^?3-10^?2 s^?1 range. The appearence rate of deethylatrazine as major oxidation product was thus also modified (k' values between 10^?4 and 10^?3 s^?1). Several by-products were detected which are either related to deethylatrazine (intermediates or oxidation products) or belong to competitive pathways. Among them, a number of formamides (a new class of atrazine ozonation products) were identified using MS and MS-MS techniques. These compounds are produced by oxidation of the N-ethylamino group likely through a non radicalar process. Deschloro-triazines were also characterized as structures whose formation specifically depends on the presence of methanol.     

芳香醛亚胺与一氧化碳的交替共聚反应

以苯乙酰基四羰基钴作为催化剂,研究了对芳香醛亚胺与一氧化碳(CO)的交替共聚反应.采用6种芳香醛亚胺单体,分别与CO进行交替共聚反应,得到了6种新的多肽类聚合物.利用核磁共振谱、红外光谱、凝胶渗透色谱(GPC)及MALDI-TOF质谱等对聚合物的结构进行了表征.探讨了芳香醛亚胺苯环上取代基的位阻效应和电子效应对聚合反应的影响.结果表明,聚合物链终止端存在3种不同类型的端基,分别具有慕尼黑酮类结构、咪唑啉类结构以及酰胺类结构,对这些端基的形成机理进行了讨论.     

Enantioselective Alternating Copolymerization of Propylene with Carbon Monoxide Using Cationic Palladium-Chiral Diphosphine Catalyst

Alternating copolymerization of (-olefins with carbon monoxide (CO) catalyzed by cationic palladium-chiral ligand complexes is of great interest due to the potential use of the resulting polymer as a new material1. Recently, enantioselective alternating copolymerization of CO with styrene has been reported by us using PdCl_2-CuCl2-chiral phosphine catalyst2. Here, we first report enantioselective alternating copolymerization of CO with propylene (P) using [(DDPPI)Pd(CH3CN)4](BF4)2 as …     

Electron transfer reactions of nickel(III) and nickel(IV) complexes

This review narrates the electron transfer reactions of various nickel(III) and nickel(IV) complexes reported during the period 1981 until today. The reactions have been categorized mainly with respect to the type of nickel complexes. The reactivity of nickel(III) complexes of macrocycles, 2,2′-bipyridyl and 1,10-phenanthroline, peptides and oxime–imine, and of nickel(IV) complexes derived from oxime–imine, oxime and miscellaneous ligands with various organic and inorganic electron donors have been included. Kinetic and mechanistic features associated with such interactions have been duly analyzed. The relevance of Marcus cross-relation equations in the delineation of the electron transfer paths has also been critically discussed.     

金属配合物和一氧化碳的反应

一氧化碳是发展可持续化学经济的重要原料。人们希望能够将一氧化碳催化转变成高附加值化学品,从而减少石油等化石资源对人类的束缚。研究均相金属配合物与一氧化碳的反应能够使人们了解一氧化碳转变及利用机理,并开发新催化剂高效地利用一氧化碳资源。本文从金属配合物与一氧化碳反应的活性点出发,分别讨论不同类型的金属配合物与一氧化碳的反应,以求让人们在分子水平上了解一氧化碳的基本反应原理;并总结了该领域存在的难点问题,展望了未来,希望更多的科研工作者投入其中,从而实现利用一氧化碳合成出各种各样的化学品和材料。     

Preparation of chelate bis(imine)nickel allyl systems by reaction of their corresponding butadiene complexes with electrophiles

The chelate 1,2-bis(imine)nickel(butadiene) complex 4a (chelate ligand derived from condensation of biacetyl with 2,6-diisopropylaniline) adds the strong Lewis acid B(C₆F₅)₃ at the terminal carbon atom of the butadiene ligand to yield the dipolar substituted π-allyl-type betaine complex (lig)Ni[η³-C₃H₄-CH₂B(C₆F₅)₃] (Z-6a). At 90 °C the kinetically formed product equilibrated with its E-6a isomer. Similarly, 4a adds the boron Lewis acid (pyrrolyl)B(C₆F₅)₂ to yield the corresponding neutral dipolar π-allyl betaine complex Z-7a, that slowly equilibrated with E-7a over several hours at ambient temperature. Protonation of the butadiene ligand of complex 4a was achieved by treatment with the neutral Brønsted acid (2H-pyrrol)B(C₆F₅)₃ to yield the [(lig)Ni(η³-crotyl)⁺][(pyrrolyl)B(C₆F₅)₃⁻] salt 9a (Z-/E-9a ratio=90:10 upon preparation). At 298 K this salt rearranged to a 5:95 mixture of Z-9a/E-9a with a Gibbs activation energy of ΔG^‡ (298 K)=22.3±0.2 kcal mol⁻¹. Complex 4a added [Ph₃C⁺] to the butadiene ligand to yield the salt [(lig)Ni(η³-C₃H₄-CH₂CPh₃)⁺][B(C₆F₅)₄⁻] (Z-12a), that proved isomerically stable under the applied reaction conditions. Similar reactions were carried out starting from the acenaphthylene 1,2-dione derived chelate bis(imine)Ni(butadiene) complex 4b. The systems 6, 7, 9 and 12 were found to be active ethene polymerization catalysts in the presence of Al(i-Bu)₃.     

泡沫镍及负载型镍催化剂制备纳米碳纤维层的研究

纳米碳纤维可用在催化材料、储氢材料、及纳米电子器件等方面。本文对用泡沫镍及负载型镍催化剂催化分解乙烯或丙烯制备纳米碳纤维进行了研究。利用X射线衍射仪、物理吸附仪、扫描电镜进行了分析表征,并考察了催化剂、碳源、生长温度对纳米碳纤维生长量、形貌、结构的影响。结果表明:在生长温度450℃,乙烯流率30mL/m in的条件下,负载型镍催化剂纳米碳纤维的生长量要高出泡沫镍3~6倍,负载型镍催化剂制备的纳米碳纤维直径为40~60纳米,小于泡沫镍的情况。泡沫镍催化分解乙烯制备纳米碳纤维时,纳米碳纤维的生长量和平均直径随温度的降低而逐渐减小。纳米碳纤维在泡沫镍上的最低生长温度为420℃,在低于480℃生长纳米碳纤维时泡沫镍的骨架结构不会被破坏,由此制备的纳米碳纤维在新型结构催化材料中有很好的的应用前景。     

钯-稀土催化一氧化碳和苯乙烯交替共聚反应

 利用稀土钇盐或钕盐和乙酸钯组成的催化体系催化一氧化碳和苯乙烯共聚,合成了聚(1-氧代-2-苯基丙撑). 用元素分析、红外光谱、示差扫描量热、热重分析及X射线光电子能谱(XPS)等方法对共聚产物进行了表征. 测试结果表明,共聚物为一氧化碳和苯乙烯的线性交替共聚产物,其玻璃化温度为235 ℃,熔点为250 ℃,分解温度为325 ℃,且用XPS未检测到聚合物中含有残留的金属. 同时考察了催化剂组分2,2′-联吡啶、对甲苯磺酸和对苯醌及溶剂甲醇等的用量对共聚反应的影响,并对聚合反应条件进行了优化. 在优化的反应条件下稀土与钯组成的复合催化剂对一氧化碳和苯乙烯交替共聚的催化活性可达1200 g/(g·h).     

Bifunctional Catalysts Containing Zn(II) and Imidazolium Salt Ionic Liquids for Chemical Fixation of Carbon Dioxide

Zn(II) can efficiently promote the catalytic performance of imidazolium salt ionic liquids (imi-ILs) for the chemical fixation of CO₂ into epoxides. To obtain sustainability, immobilized bifunctional catalysts containing both imi-ILs and Zn(II) were prepared using bimodal mesoporous silica (BMMs) as carrier, through grafting of Zn(OAc)₂ and 1-(trimethoxysilyl)propyl-3-methylimidazolium chloride (Si-imi) separately in the nanopores. The catalysts, named as BMMs−Zn&ILs, were identified as efficient catalysts for cycloaddition reaction of CO₂ into epoxides under solvent-free conditions. BMMs−Zn&ILs showed good catalytic activity, which increased with the increase of the molar ratio of Zn(II) to Si-imi. As a comparison, different catalytic systems including homogeneous imi-IL, BMMs-ILs and BMMs−Zn were studied to demonstrate different cooperation behaviors. Furthermore, the kinetics studies of homogeneous and heterogeneous bifunctional catalysts were employed to confirm the differences, as well as to support the proposed cooperative catalysis mechanism in the nanopores.     

Behavior of a nickel electrode in the presence of carbon monoxide

The electrochemical behavior of a nickel electrode with limited volume (LVE) electrodeposited as a thin layer on gold has been studied. The influence of the gold matrix on the electrochemical Ni electrode behavior has been considered. The electrosorption and oxidation of carbon monoxide on the Ni surface and its influence on hydrogen sorption has also been demonstrated. Received: 21 May 1997 / Accepted: 9 June 1997     

AlOOH结构对甲醇和一氧化碳反应性能的影响

利用水热法制备了3种AlOOH催化剂,对其进行了表征,并用于催化甲醇和一氧化碳反应.结果表明,适宜的AlOOH结构有利于催化甲醇和一氧化碳反应生成高选择性(≥97.28%)的乙醛,且AlOOH结构的差异会导致反应产物分布出现明显区别.其中,结晶度高、孔径较大、能提供CO解离吸附中心且表面具有适宜酸碱性的AlOOH催化剂表现出高的乙醛选择性,推测乙醛的生成是通过中间体CH_3与HCO的偶联实现的.     

Correlating Metal Redox Potentials to Co(III)K(I) Catalyst Performances in Carbon Dioxide and Propene Oxide Ring Opening Copolymerization

Carbon dioxide copolymerization is a front-runner CO₂ utilization strategy but its viability depends on improving the catalysis. So far, catalyst structure-performance correlations have not been straightforward, limiting the ability to predict how to improve both catalytic activity and selectivity. Here, a simple measure of a catalyst ground-state parameter, metal reduction potential, directly correlates with both polymerization activity and selectivity. It is applied to compare performances of 6 new heterodinuclear Co(III)K(I) catalysts for propene oxide (PO)/CO₂ ring opening copolymerization (ROCOP) producing poly(propene carbonate) (PPC). The best catalyst shows an excellent turnover frequency of 389 h⁻¹ and high PPC selectivity of >99 % (50 °C, 20 bar, 0.025 mol% catalyst). As demonstration of its utility, neither DFT calculations nor ligand Hammett parameter analyses are viable predictors. It is proposed that the cobalt redox potential informs upon the active site electron density with a more electron rich cobalt centre showing better performances. The method may be widely applicable and is recommended to guide future catalyst discovery for other (co)polymerizations and carbon dioxide utilizations.