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51.
Farah Naz Bibimaryam Mousavi Zhixiong Luo Christia Jabbour Philippe M. Heynderickx Somboon Chaemchuen Francis Verpoort 《应用有机金属化学》2019,33(5)
A series of spray dried zeolitic imidazolate frameworks (ZIFs = ZIF‐8, ZIF‐67, and Zn/Co‐ZIF) are used as a catalyst for the bulk ring‐opening polymerization of δ‐valerolactone without any co‐catalyst to generate polyvalerolactone. Interestingly, using the same catalyst under the same reaction conditions could manipulate the structure of the product polymer, and thus its physical properties. Thus, using a dried substrate leads to the formation of the cyclic polymer while a linear polymer was formed on using the commercially available substrate. An activated monomer mechanism has been suggested where the propagating zinc alkoxide undergoes an intramolecular transesterification to release cyclic or linear polyvalerolactone. The ROP of δ‐VL without drying shows that the polymeric zwitterions have little tendency to cyclize in the presence of moisture. At 140 °C, ZIF‐8 shows a superior catalytic activity resulting in the production of cyclic polyvalerolactone having a high molecular weight as compared to ZIF‐67 or Zn/Co‐ZIF due to the presence of highly active sites. The catalyst could be recycled and reused without any significant loss of catalytic activity. 相似文献
52.
A palladium–fibroin complex (Pd/Fib.) was prepared by the addition of sonicated fibroin fiber in water to palladium acetate solution. Pd (OAc)2 was absorbed by fibroin and reduced with NaBH4 at room temperature to the Pd(0) nanoparticles. Powder‐X‐ray diffraction, scanning electron microscopy–energy‐dispersive X‐ray spectroscopy, Fourier transform‐infrared, CHN elemental analysis and inductively coupled plasma‐atomic emission spectroscopy were carried out to characterize the Pd/Fib. catalyst. Catalytic activity of this finely dispersed palladium was examined in the Heck coupling reaction. The catalytic coupling of aryl halides (‐Cl, ‐Br, ‐I) and olefins led to the formation of the corresponding coupled products in moderate to high yields under air atmosphere. A variety of substrates, including electron‐rich and electron‐poor aryl halides, were converted smoothly to the targeted products in simple procedure. Heterogeneous supported Pd catalyst can be recycled and reused several times. 相似文献
53.
Niloufar Afzali Reihaneh Kardanpour Farnaz Zadehahmadi Shahram Tangestaninejad Majid Moghadam Valiollah Mirkhani Adam Mechler Iraj Mohammadpoor‐Baltork Mehrnaz Bahadori 《应用有机金属化学》2019,33(11)
A novel heterogeneous nanocatalyst was established by supporting molybdenum (VI) on Zr6 nodes in the structure of the well‐known UiO‐66 metal–organic framework (MOF). The structure of the UiO‐66 before and after Mo (VI) immobilization was confirmed with XRD, DR‐FTIR and UV–vis spectroscopy, and the presence and amount of Mo (VI) was identified by X‐ray photoelectron spectroscopy and inductively coupled plasma atomic emission spectroscopy. TEM imaging confirmed the absence of Mo clusters on the MOF surface, while SEM confirmed that the appearance of the MOF has not changed upon immobilizing the Mo (VI) catalyst. BET adsorption measurements were used to confirm the porosity of the catalyst. The catalytic activity of this heterogeneous catalyst was investigated in oxidation of sulfides with H2O2 in acetonitrile and oxidative desulfurization of dibenzothiophene. Easy work up, convenient and steady reuse and high activity and selectivity are prominent properties of this new hybrid material. 相似文献
54.
This paper considers the formation of dead zones in the porous catalyst pellets due to the chemical reaction and diffusion. We established and investigated the model with nonisothermal reaction of fractional order and activated temperature-dependent diffusivity. The effects of process parameters, catalyst shape, and reaction and diffusion parameters on the formation of the dead zone are studied numerically and characterized by the critical Thiele modulus. The lower bounds for the critical Thiele modulus are derived analytically in terms of process parameters for exothermic and endothermic reactions and verified numerically. The critical Thiele modulus increases with increasing Arrhenius number for diffusion and decreasing Arrhenius number for reaction in the case of exothermic reactions, whereas the opposite trends hold for the endothermic reactions. The critical Thiele modulus also increases with increasing fractional reaction order as well as with decreasing energy generation function, and increasing Biot numbers for heat and mass transfer. Moreover, the critical Thiele modulus is the highest for spherical pellets and the lowest for pellets with planar shape. 相似文献
55.
In the present study, biosynthesis of CuO nanoparticles using a rapid, eco‐friendly, cost‐effective and efficient method has been reported employing aqueous Euphorbia maculata extract as mild, renewable and non‐toxic reducing and capping agents without adding any surfactants. The biogenic and green method has some benefits compared to conventional physical and chemical methods. It is simple, cheap and environmentally friendly. The biosynthesized CuO NP displayed a color change pattern (from sky blue to black) on preparation and presented its respective broad peak at 365 nm, which was analyzed by UV–Vis spectroscopy. Using the FT‐IR analysis, biomolecules in E. maculata extract which are responsible for bioreduction activity and synthesize of CuO NP, were identified. The XRD, EDX and FESEM results confirmed the successful synthesis of CuO nanoparticles of 18 nm sizes, with spherical and sponge crystal structure. The catalytic activity of biosynthesized CuO NPs was studied in C‐S cross‐coupling reaction. This method has the advantages of high yields, easy work‐up, and simple reusability. The recovered CuO NP can be reused four times without any considerable loss of its catalytic activity. 相似文献
56.
57.
Tae Hee Kim Hyun Mo Lee Hee Soo Park Sung Dong Kim Su Jin Kwon Atsushi Tahara Hideo Nagashima Bun Yeoul Lee 《应用有机金属化学》2019,33(4)
The original Sasol catalytic system for ethylene tetramerization is composed of a Cr source, a PNP ligand, and MAO (methylaluminoxane). The use of expensive MAO in excess has been a critical concern in commercial operation. Many efforts have been made to replace MAO with non‐coordinating anions (e.g., [B(C6F5)4]?); however, most of such attempts were unsuccessful. Herein, an extremely active catalytic system that avoids the use of MAO is presented. The successive addition of two equivalent [H(OEt2)2]+[B(C6F5)4]? and one equivalent CrCl3(THF)3 to (acac)AlEt2 and subsequent treatment with a PNP ligand [CH3(CH2)16]2C(H)N(PPh2)2 ( 1 ) yielded a complex presumably formulated as [ 1 ‐CrAl (acac)Cl3(THF)]2+[B(C6F5)4]?2, which exhibited high activity when combined with iBu3Al (1120 kg/g‐Cr/h; ~4 times that of the original Sasol system composed of Cr (acac)3, iPrN(PPh2)2, and MAO). Via the introduction of bulky trialkylsilyl substituents such as –SiMe3, –Si(nBu)3, or –SiMe2(CH2)7CH3 at the para‐position of phenyl groups in 1 (i.e., by using [CH3(CH2)16]2C(H)N[P(C6H4‐p‐SiR3)2]2 instead of 1 ), the activities were dramatically improved, i.e., tripled (2960–3340 kg/g‐Cr/h; more than 10 times that of the original Sasol system). The generation of significantly less PE (<0.2 wt%) even at a high temperature is another advantage achieved by the introduction of bulky trialkylsilyl substituents. NMR studies and DFT calculations suggest that increase of the steric bulkiness on the alkyl‐N and P‐aryl moieties restrict the free rotation around (alkyl)N–P (aryl) bonds, which may cause the generation of more robust active species in higher proportion, leading to extremely high activity along with the generation of a smaller amount of PE. 相似文献
58.
Dr. Wenyan Hao Yuchen Sha Dr. Yi Deng Yi Luo Li Zeng Shan Tang Dr. Yue Weng Prof. Dr. Chien-Wei Chiang Prof. Dr. Aiwen Lei 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(19):4931-4934
An in situ generated oxidation species of nickel quinolinylpropioamide intermediate was produced. Characterization by X-ray absorption near edge structure (XANES) and EPR provides complementary insights into this oxidized nickel species. With aliphatic amides and isocyanides as substrates, a nickel-catalyzed facile synthesis of structurally diverse five-membered lactams could be achieved. 相似文献
59.
Philip Eckert Prof. Dr. Michael G. Organ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(69):15751-15754
The impact of LiBr and ZnBr2 salts on the Negishi coupling of alkylZnBr and dialkylzinc nucleophiles with both electron-rich and -poor aryl electrophiles has been examined. Focusing only on the more difficult coupling of deactivated (electron-rich) oxidative addition partners, LiBr promotes coupling with BuZnBr, but does not have such an effect with Bu2Zn. The presence of exogenous ZnBr2 shuts down the coupling of both BuZnBr and Bu2Zn, which has been shown before with alkyl electrophiles. Strikingly, the addition of LiBr to Bu2Zn reactions containing exogenous ZnBr2 now fully restores coupling to levels seen without any salt present. This suggests that there is a very important interaction between LiBr and ZnBr2. It is proposed that Lewis acid adducts are forming between ZnBr2 and the electron-rich Pd0 centre and the bromide from LiBr forms inorganic zincates that prevent the catalyst from binding to ZnBr2. This idea has been supported by catalyst design as chlorinating the backbone of the NHC ring of Pd-PEPPSI-IPent to produce Pd-PEPPSI-IPentCl catalyst now gives quantitative conversion, up from a ceiling of only 50 % with the former catalyst. 相似文献
60.
Palladium catalyzed domino C-H functionalization reaction of arylaldehyde with dihaloarene has been developed to access 9-flourenone molecules. Bidentate ligand assisted strategy, single step reaction, high yield and excellent functional group tolerance make this method concise and effective for the synthesis of 9-flourenone. In addition, proposed method has been successfully employed to synthesise Tilorone in gram scale. 相似文献