- Syntheses, structures, molecular and cationic recognitions and catalytic properties of two lanthanide coordination polymers based on a flexible tricarboxylate
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Two lanthanide coordination polymers, namely, {[La(TTTA)(H 2O)2]·2H2O}n (La-TTTA) and [Nd(TTTA)(H2O)2]·2H2O}n (Nd-TTTA) have been hydrothermally synthesized through th
- Zhu, Yu,Wang, Yan-Mei,Xu, Ji,Liu, Pan,Weththasinha,Wu, Yun-Long,Lu, Xiao-Qing,Xie, Ji-Min
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- From 1D to 3D lanthanide coordination polymers constructed with pyridine-3,5-dicarboxylic acid: Synthesis, crystal structures, and catalytic properties
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Three series of lanthanide coordination polymers with formula [Ln2(PDC)3(H2O)2(DMF)]·4H2O (type I) (Ln = La 1, Pr 2, Sm 3), [(CH3)2NH2][Ln2(PDC)3
- Lin, Xiao-Ming,Niu, Ji-Liang,Wen, Pei-Xian,Lu, Yan-Na,Hu, Lei,Zhang, Da-Liang,Cai, Yue-Peng
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- Bifunctional 2D Cd(II)-Based Metal-Organic Framework as Efficient Heterogeneous Catalyst for the Formation of C-C Bond
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A porous two-dimensional (2D) metal-organic framework (MOF), namely, [Cd(PBA)(DMF)]·DMF (Cd-PBA), has been solvothermally synthesized by the reaction of 5-(4-pyridin-3-yl-benzoylamino)-isophthalic acid ligand (H2PBA) and Cd(II) ions. Structural
- Hu, Lei,Hao, Gui-Xia,Luo, Hai-Dong,Ke, Chun-Xian,Shi, Guang,Lin, Jia,Lin, Xiao-Ming,Qazi, Umair Yaqub,Cai, Yue-Peng
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- Synthesis of 2D and 3D MOFs with tuneable Lewis acidity from preformed 1D hybrid sub-domains
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Novel MOF-type materials with different morphologies based on assembled 1D organic-inorganic sub-domains were prepared using specific monodentate benzylcarboxylate spacers with functional substituents in the para-position as structure modulating agents. T
- Moreno, José María,Velty, Alexandra,Díaz, Urbano,Corma, Avelino
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- Hollow silica nanosphere having functionalized interior surface with thin manganese oxide layer: Nanoreactor framework for size-selective Lewis acid catalysis
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A novel selective nanoscale etching process that generated a well defined hollow nanostructure was developed by treating manganese oxide nanoparticles with a hydroxylamine solution. This selective etching process was used for exploiting a novel method of differentially functionalizing the internal surface of a hollow silica shell with a catalytically active Mn3O 4 layer and creating a novel nanoreactor framework. The nanoreactor fabricated by the newly developed method catalyzed the cyanosilylation reactions of various aromatic aldehydes with size and shape selectivity. Moreover, the substrate selectivity in the cyanosilylation reactions was efficiently tuned by modifying the outer silica shell with silane coupling reagents.
- Anisur, Rahman Md,Shin, Jongmin,Choi, Hyung Ho,Yeo, Kyung Min,Kang, Eun Joo,Lee, In Su
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- Thermal response, catalytic activity, and color change of the first hybrid vanadate containing Bpe guest molecules
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Four isomorphic compounds with formula [{Co2(H 2O)2(Bpe)2}(V4O12)] ·4H2O·Bpe, CoBpe 1; [{CoNi(H2O) 2(Bpe)2}(V4O12)]·4H 2O·Bpe, CoNiBpe 2; [{Co0.6Ni1.4(H 2O)2(Bpe)2}(V4O12)] ·4H2O·Bpe, NiCoBpe 3; and [{Ni2(H 2O)2(Bpe)2}(V4O12)] ·4H2O·Bpe, NiBpe 4, have been obtained by hydrothermal synthesis. The crystal structures of CoBpe 1 and NiBpe 4 were determined by single-crystal X-ray diffraction (XRD). The Rietveld refinement of CoNiBpe 2 and NiCoBpe 3 XRD patterns confirms that those are isomorphic. The compounds crystallize in the P1I?... space group, exhibiting a crystal structure constructed from inorganic layers pillared by Bpe ligands. The crystal structure contains intralayer and interlayer channels, in which the crystallization water molecules and Bpe guest molecules, respectively, are located. The solvent molecules establish a hydrogen bonding network with the coordinated water molecules. Thermodiffractometric and thermogravimetric studies showed that the loss of crystallization and coordinated water molecules takes place at different temperatures, giving rise to crystal structure transformations that involve important reduction of the interlayer distance, and strong reduction of crystallinity. The IR, Raman, and UV-vis spectra of the as-synthesized and heated compounds confirm that the structural building blocks and octahedral coordination environment of the metal centers are maintained after the structural transformations. The color change and reversibility of the water molecules uptake/removal were tested showing that the initial color is not completely recovered when the compounds are heated at temperatures higher than 200 C. The thermal evolution of the magnetic susceptibility indicates one-dimensional antiferromagnetic coupling of the metal centers at high temperatures. For NiCoBpe 3 and NiBpe 4 compounds magnetic ordering is established at low temperatures, as can be judged by the maxima observed in the magnetic susceptibilities. CoNiBpe 2 was proved as catalyst being active for cyanosilylation reactions of aldehydes.
- Fernández De Luis, Roberto,Urtiaga, M. Karmele,Mesa, José L.,Larrea, Edurne S.,Iglesias, Marta,Rojo, Teófilo,Arriortua, María I.
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- Syntheses, structures and catalytic properties of organic-inorganic hybrid materials constructed from Evans-Showell-type polyoxometalates and zinc-organic coordination units
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Four new organic-inorganic hybrid compounds based on the polyoxoanion [Co2Mo10H4O38]6-, namely [Zn2(H2O)5(4,4′-bipy)3]H2[Co2Mo10
- Fei, Fei,An, Haiyan,Xu, Tieqi,Meng, Changgong
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- Synthesis, crystal structures, luminescence properties and catalytic application of lanthanide(III) piperidine dithiocarbamate complexes
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A series of lanthanide(III) piperidine dithiocarbamate complexes [Ln(Pip-Dtc)3(Phen)] [where Ln = La(III), Ce(III), Pr(III), Nd(III), Sm(III), Gd(III), Tb(III), Dy(III), Er(III); Pip-Dtc = piperidine dithiocarbamate and Phen = 1,10-phenanthroline] has been synthesized and structurally characterized by analytical and various spectral techniques such as FT-IR, UV-Vis and 1H NMR. The molecular structure of [Pr(Pip-Dtc)3(Phen)], [Nd(Pip-Dtc)3(Phen)] and [Sm(Pip-Dtc)3(Phen)] complexes were determined by single crystal X-ray diffraction studies. The binding of the Pip-Dtc to the metal center involves two sulfur atoms and Phen through two nitrogen atoms. The metal center is octa-coordinated by three Pip-Dtc and one Phen ligands. The coordination geometry around Ln(III) ion is distorted dodecahedron. The photoluminescence properties of Sm(III), Pr(III), Tb(III), Dy(III) complexes indicated that the emission intensity depend on the nature of the metal ion, ligand and polarity of the medium. These complexes exhibited good to excellent catalytic activity in trimethylsilyl cyanation of benzaldehyde.
- Pitchaimani, Ponnuchamy,Lo, Kong Mun,Elango, Kuppanagounder P.
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- Improving the porosity and catalytic capacity of a zinc paddlewheel metal-organic framework (MOF) through metal-ion metathesis in a single-crystal-to-single-crystal fashion
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Zinc paddlewheel metal-organic frameworks (MOFs) frequently exhibit low stability or complete collapse upon the removal of axial ligands. Hence, there are very few reports on gas adsorption of zinc paddlewheel MOFs. In this work, the N2 and Hs
- Yang, Jie,Wang, Xiaoqing,Dai, Fangna,Zhang, Liangliang,Wang, Rongming,Sun, Daofeng
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- Straightforward synthesis and catalytic applications of rigid N,O-type calixarene ligands
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Here, we report a simple one-step access to new rigid N,O-calixarene ligands which is based on copper-catalyzed amination at the lower rim. We also present the coordination properties of these ligands with some main group and transition metals leading to
- Rawat, Varun,Press, Konstantin,Goldberg, Israel,Vigalok, Arkadi
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- Lanthanide-Based Metal-Organic Frameworks Containing "v-Shaped" Tetracarboxylate Ligands: Synthesis, Crystal Structures, "naked-Eye" Luminescent Detection, and Catalytic Properties
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Three lanthanide-based metal-organic frameworks, [Tb(HMDIA)(H2O)3]·H2O (Tb-MDIA), [Ho(HMDIA)(H2O)3]·(H2O)2 (Ho-MDIA), and [Nd(HMDIA)(H2O)3]·(H2O)
- Wu, Pengyan,Xia, Lingling,Huangfu, Mengjie,Fu, Fubin,Wang, Mengqiu,Wen, Bingxin,Yang, Ziyun,Wang, Jian
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- Insight into the correlation between net topology and ligand coordination mode in new lanthanide MOFs heterogeneous catalysts: A theoretical and experimental approach
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Three new families of compounds were obtained as pure phases, with different lanthanide cations and the 3,5-disulfobenzoic acid (3,5-DSB). The hydrothermal synthesis conditions influence on structural type obtained was studied. The structural type RPF-21 corresponds to the compound [Ln(3,5-DSB)(H2O)5] (Ln = La, Pr, Nd); RPF-22 to the compound [Ln(3,5-DSB)(H2O)3] (Ln = La, Pr, Nd, Sm, and Eu), and RPF-23 to the compound [Ln3(3,5-DSB)2(OH) 3(H2O)3] (Ln = Pr, Nd, and Eu). The dimensionality and the topology of the compounds are determined by the sulfonate group coordination modes; RPF-23 presents a new type of topology. Computational studies have determined the relative energies for those compounds that coexist under certain hydrothermal conditions, and they have brought some light to the thermodynamic or kinetic control that drives each reaction. The new materials were tested as catalysts in cyanosilylation reaction (CSR) of aldehydes under solvent-free conditions. The three of them catalyze the CSRs within 4 h, and a remarkable difference in activity is found between RPF-21 and the other two materials. The catalytic activity mainly depends on the network structure, with very little influence of the lanthanide cation. The mechanism includes, probably, a displacement of the catalyst labile water molecules by aldehyde before catalysts activation and reaction.
- Dvries, Richard F.,De La Pena-Oshea, Victor A.,Snejko, Natalia,Iglesias, Marta,Gutierrez-Puebla, Enrique,Monge, M. Angeles
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- O,N-Heterocyclic germylenes as efficient catalysts for hydroboration and cyanosilylation of benzaldehyde
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New monomeric O,N-heterocyclic germylene AdAPGe (1) based on 4,6-di-tert-butyl-N-adamantyl-o-aminophenol is synthesized and structurally characterized. Germylene 1 in the crystal demonstrates weak Ge?Ge interactions between adjacent molecules. The redox activity of compound 1 and its known analogs PhAPGe (2), t-BuAPGe (3) was studied using cyclic voltammetry and chemical oxidation by the phenoxy radical. Germylene 1, as opposed to 2 and 3, was found to form a relatively stable o-iminosemiquinonate moiety during oxidation. The last one was detected by EPR spectroscopy in toluene solution at low temperatures. The catalytic activity of germylenes 1-3 and dippAPGe (4) (dipp-2,6-di-isopropylphenyl) towards hydroboration and cyanosilylation of benzaldehyde was examined. Germylene 1 demonstrates the most potent promoter properties for such reactions, which allowed cyanosilylation and hydroboration of aldehyde under mild conditions with excellent conversion quickly. Theoretical studies were performed to establish the mechanism, and different reaction routes were examined. According to the DFT (B3LYP/def2-SVP) calculation, cyanosilylation and hydroboration processes are initiated by coordinating TMSCN or HBpin with the catalyst. The followed reaction with aldehyde leads to the resulting products.
- Arsenyeva, Kseniya V.,Pashanova, Kira I.,Trofimova, Olesya Yu.,Ershova, Irina V.,Chegerev, Maxim G.,Starikova, Alyona A.,Cherkasov, Anton V.,Syroeshkin, Mikhail A.,Kozmenkova, Anna Ya.,Piskunov, Alexandr V.
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p. 11758 - 11767
(2021/07/12)
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- Sodium squaraine hexahydrate complex
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The invention relates to a sodium squaraine hexahydrate complex, a synthesis method comprises the following steps: weighing 0.6621 g of squaric acid, 2.6128 g of ammonium formate and 100 ml of absolute methanol in a 250 mL round-bottom flask, heating, stirring and refluxing for 48 hours, stopping reaction, adding 10 mL of a 1M HCl solution, extracting with 3*15 mL of dichloromethane, washing the combined extract with 15 mL of a 12 M NaOH solution again, and extracting with 3*15 mL of dichloromethane; and carrying out rotary evaporation on an extracting solution and carrying out column chromatography separation to obtain the crystal complex. According to the application of the sodium squaraine hexahydrate complex (I), the sodium squaraine hexahydrate complex (I) is used as a catalyst in theaddition reaction of benzaldehyde and trimethylsilyl cyanide and shows a certain catalytic performance, and the conversion rate of the sodium squaraine hexahydrate complex reaches 34.8%.
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Paragraph 0031-0033
(2021/03/03)
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- Application of an Electrochemical Microflow Reactor for Cyanosilylation: Machine Learning-Assisted Exploration of Suitable Reaction Conditions for Semi-Large-Scale Synthesis
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Cyanosilylation of carbonyl compounds provides protected cyanohydrins, which can be converted into many kinds of compounds such as amino alcohols, amides, esters, and carboxylic acids. In particular, the use of trimethylsilyl cyanide as the sole carbon source can avoid the need for more toxic inorganic cyanides. In this paper, we describe an electrochemically initiated cyanosilylation of carbonyl compounds and its application to a microflow reactor. Furthermore, to identify suitable reaction conditions, which reflect considerations beyond simply a high yield, we demonstrate machine learning-assisted optimization. Machine learning can be used to adjust the current and flow rate at the same time and identify the conditions needed to achieve the best productivity.
- Sato, Eisuke,Fujii, Mayu,Tanaka, Hiroki,Mitsudo, Koichi,Kondo, Masaru,Takizawa, Shinobu,Sasai, Hiroaki,Washio, Takeshi,Ishikawa, Kazunori,Suga, Seiji
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supporting information
p. 16035 - 16044
(2021/09/02)
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- Valmet Chiral Schiff-Base Ligands And Their Copper(II) Complexes as Organo, Homogeneous and Heterogeneous Catalysts for Henry, Cyanosilylation and Aldol Coupling Reactions
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Cyanosilylation, aldol coupling and asymmetric Henry reactions were carried out with L- and D-valmet ligands in different configurations: i) coordinated to sodium ions, as organocatalysts, with week base properties, ii) complexes with copper(II), as homogeneous catalysts, and iii) immobilized copper(II) complexes onto graphene oxide (GO) as heterogeneous catalysts. For the reaction of benzaldehyde and nitromethane in water these afforded an asymmetric Henry reaction, with a spectacular increase of the conversion and ee (92.5 and 95.8 %, respectively) after the deposition on GO. Ligand complexed copper was also effective for cyanosilylation and Aldol coupling reaction.
- Arora, Zinnia,Eftemie, Diana-Ioana,Spinciu, Adela,Maxim, C?t?lin,Hanganu, Ana-Maria,Tudorache, Madalina,Cojocaru, Bogdan,Pavel, Octavian D.,Granger, Pascal,Andruh, Marius,Parvulescu, Vasile I.
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p. 4634 - 4644
(2021/09/08)
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- Cyanosilylation of carbonyl compounds catalyzed by half-sandwich (η6-p-cymene) Ruthenium(II) complexes bearing heterocyclic hydrazone derivatives
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A new class of half-sandwich (?6-p-cymene) ruthenium(II) complexes supported by heterocyclic hydrazone derivatives of general formula [Ru(?6-p-cymene)(Cl)(L)] where L represents N’-((1H-pyrrol-2-yl)methylene)furan-2-carbohydrazide (L
- Alves, Luis G.,Bharathi, Madheswaran,Indira, Sekar,Martins, Ana M.,Shanmuga Bharathi, Kuppannan,Vinoth, Govindasamy
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- Synthesis of cyanooxovanadate and cyanosilylation of ketones
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The cyanosilylation was performed by using metavanadate catalysts, and in situ measurements revealed the formation of [VO2(CN)3]2- and [VO4TMS2]- under reaction conditions. The reaction of [VO2(CN)3]2-, trimethylsilyl cyanide (TMSCN), and water afforded [
- Hayashi, Yoshihito,Kawabata, Hiroko,Kikukawa, Yuji
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p. 31688 - 31692
(2021/11/30)
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- Crystal transformation in Mn(ii) metal-organic frameworks based on a one-dimensional chain precursor
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The solvothermal reaction of Mn(ii) salts and 5-((4′-(tetrazol-5′′-yl)benzyl)oxy)isophthalic acid (H3L) affords an Mn(ii) based coordination polymer Mn(H2L)2(H2O)2(1), which possesses a one-dimensiona
- Fan, Yong,Gong, Yiran,Jiang, Yansong,Liu, Rui,Wang, Li,Xu, Jianing
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p. 9540 - 9546
(2021/07/17)
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- H-Bonded and metal(ii)-organic architectures assembled from an unexplored aromatic tricarboxylic acid: structural variety and functional properties
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This study reports the application of an aromatic tricarboxylic acid, 2,5-di(4-carboxylphenyl)nicotinic acid (H3dcna) as a versatile and unexplored organic building block for assembling a new series of metal(ii) (M = Co, Ni, Zn, Fe, and Mn) complexes and coordination polymers, namely [M(Hdcna)(phen)2(H2O)]·H2O (M = Co (1), Ni (2)), [Zn(μ-Hdcna)(phen)]n(3), [Co(μ-Hdcna)(bipy)(H2O)2]n·nH2O (4), [Zn2(μ-Hdcna)2(bipy)2(H2O)4]·6H2O (5), [Zn(μ3-Hdcna)(H2biim)]n(6), [Ni2(Hdcna)2(μ-bpb)(bpb)2(H2O)4] (7), [Fe(μ4-Hdcna)(μ-H2O)]n·nH2O (8), and [Mn3(μ5-dcna)2(bipy)2(H2O)2]n·2nH2O (9). Such a diversity of products was hydrothermally prepared from the corresponding metal(ii) salts, H3dcna as a principal multifunctional ligand, and N-donor mediators of crystallization (1,10-phenanthroline, phen; 2,2'-bipyridine, bipy; 2,2'-biimidazole, H2biim; or 1,4-bis(pyrid-4-yl)benzene, bpb). The obtained products1-9were fully characterized by standard methods (elemental analysis, FTIR, TGA, PXRD) and the structures were established by single-crystal X-ray diffraction. These vary from the discrete monomers (1,2) and dimers (5,7) to the 1D (3,4,6) and 2D (8,9) coordination polymers (CPs). Structural and topological characteristics of hydrogen-bonded or metal-organic architectures in1-9were highlighted, revealing that their structural multiplicity depends on the type of metal(ii) source and crystallization mediator. Thermal stability as well as luminescent, magnetic, or catalytic properties were explored for selected compounds. In particular, the zinc(ii) derivatives3,5, and6were applied as efficient heterogeneous catalysts for the cyanosilylation of aldehydes with trimethylsilyl cyanide at room temperature. The catalytic reactions were optimized by tuning the different reaction parameters (solvent composition, time, catalyst loading) and the substrate scope was also explored. Compound5revealed superior catalytic activity leading to up to 75% product yields, while maintaining its original performance upon recycling for at least four reaction cycles. Finally, the obtained herein products represent the unique examples of coordination compounds derived from H3dcna, thus opening up the use of this multifunctional tricarboxylic acid for generating complexes and coordination polymers with interesting structures and functional properties.
- Gu, Jin-Zhong,Kirillov, Alexander M.,Kirillova, Marina V.,Wan, Shi-Mao
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p. 7197 - 7209
(2020/06/04)
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- Role of aromatic: Vs. aliphatic amine for the variation of structural, electrical and catalytic behaviors in a series of silver phosphonate extended hybrid solids
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Four inorganic-organic hybrid silver phosphonate compounds, [Ag(C10H8N2)(H4hedp)] (1), [Ag2(C10H8N2)(H3hedp)]·2H2O (2), [C4H12N2][Ag4(H2hedp)2] (3) and [C4H12N2][Ag10(H2hedp)4(H2O)2]·2H2O (4) (H5hedp = 1-hydroxyethane-1,1-diphosphonic acid), have been pre
- Rom, Tanmay,Paul, Avijit Kumar
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supporting information
p. 13618 - 13634
(2020/10/26)
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- Three Coordinated Organoaluminum Cation for Rapid and Selective Cyanosilylation of Carbonyls under Solvent-Free Conditions
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The well-defined three coordinated electronically unsaturated cationic organoaluminum complex [({(2,6-iPr2C6H3N)P(Ph2)}2N)AlMe]+[MeB(C6F5)3]? (1), has been utilized to catalyze the cyanosilylation of aldehydes and ketones under mild and solvent-free conditions. Moreover, catalyst 1 showed high chemoselective cyanosilylation of aldehydes over ketones, nitriles and olefins. The multinuclear NMR investigations revealed that cyanosilylation proceeds via Lewis adduct formation between 1 and TMSCN thereby activating TMSCN (Si-CN bond) followed by nucleophilic attack of the carbonyl oxygen at the Si center of the activated silane and formation of the product.
- Bhandari, Mamta,Prashanth, Billa,Rawat, Sandeep,Singh, Sanjay
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- Minimizing solvent waste in catalytic reactions in highly recyclable hydrocarbon solvents
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This paper describes chemistry using organocatalysts in hydrocarbon solvents that minimizes solvent waste by using inexpensive, non-volatile, relatively inflammable, and easily recyclable poly(α-olefin)s (PAOs) as hydrocarbon solvents. These studies show that when substrates have limited solubility in PAO solvents, this issue can be addressed by adding a small amount of a cosolvent. Kinetic studies were also carried out and show that reactions carried out in PAOs are kinetically comparable to reactions in conventional non-recyclable hydrocarbon solvents. A range of strategies that separate and isolate products from reactions in PAOs using a polyisobutylene (PIB)-supported DMAP catalyst have been studied using four different catalytic reactions. In the most general procedure, the PAO phase containing a PIB-bound catalyst is separated from products by low energy liquid/liquid gravity separation. This can be accomplished using a minimal amount of a polar solvent. In another example, the product's low solubility leads to it precipitating during the reaction. In this case, a simple filtration recycles the PAO and a PIB-bound DMAP catalyst. We have demonstrated that the PAO phase containing a PIB bound DMAP catalyst can be recycled for at least 10 cycles without loss of activity. Our studies further showed that leaching of the PAO phase into polar solvents was orders of magnitude less than conventional hydrocarbon solvents such as heptane. The result is that the overall solvent waste generation is lower than for the same reaction carried out in conventional solvents.
- Bergbreiter, David E.,Killough, James M.,Thavornpradit, Sopida
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p. 4248 - 4256
(2020/06/21)
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- The direct trifluoromethylsilylation and cyanosilylation of aldehydes: via an electrochemically induced intramolecular pathway
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The initiator-free electrochemical trifluoromethylsilylation and cyanosilylation of aldehydes were developed in an undivided cell. A DFT study reveals that the direct cathodic activation of trimethylsilyl reagents significantly released the congestion around the 'Si' atom, allowing the Si-O bond affinity to form concerted anion intermediates with aldehydes. Thus, intramolecular -CF3 and -CN migration make the reactions much easier to carry out without initiators.
- Yang, Hui,Shen, Yongli,Xiao, Zihui,Liu, Caiyan,Yuan, Kedong,Ding, Yi
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supporting information
p. 2435 - 2438
(2020/03/06)
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- Two polyoxoniobates-based ionic crystals as Lewis base catalysts for cyanosilylation
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Two transition-metal containing heteropolyniobates, H[Ni(en)3]5[VNb12O40(VO)2]·15H2O (1) and H3[Cu(en)2]4[VNb12O40(VO)2]·13
- Li, Shujun,Ji, Panpan,Han, Shangning,Hao, Zhaomin,Chen, Xuenian
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- Supported Ionic Liquid-Like Phases (SILLPs) as Immobilised Catalysts for the Multistep and Multicatalytic Continuous Flow Synthesis of Chiral Cyanohydrins
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Supported Ionic Liquid-Like Phases have been found to be efficient organocatalysts for the synthesis of cyanohydrin esters under solvent-free conditions by an “electrophile-nucleophile dual activation” based on hydrogen bond formation. The combination of
- Peris, Edgar,Porcar, Raúl,Burguete, María Isabel,García-Verdugo, Eduardo,Luis, Santiago V.
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p. 1955 - 1962
(2019/03/13)
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- Layered double hydroxides (LDHs): As efficient heterogeneous catalyst for the cyanosilylation of aromatic aldehydes
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We report the first application of Layered Double Hydroxides (LDHs) as efficient and novel heterogeneous catalyst for the cyanosilylation of aldehydes with excellent yields and simple work up. The reaction between different aldehydes with electron-withdra
- Afi, Fahimeh,Mokhtari, Javad,Tahoori, Fatemeh
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- Solvent-free cyanosilylation of aromatic and heteroaryl aldehydes catalyzed by a cationic iron N-heterocyclic carbene complex at ambient temperature under UV irradiation
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The cyanosilylation of aromatic aldehydes and heteroaryl aldehydes with trimethylsilyl cyanide (TMSCN) is efficiently catalyzed by an iron complex of the type {[3-isopropyl-1-(1R-phenylethyl)imidazol-2-ylidene]Fe(CO)2}I (3) in presence of UV li
- Kumar, Dharmendra,Prakasham,Gangwar, Manoj Kumar,Ghosh, Prasenjit
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supporting information
(2019/08/07)
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- Regio- and stereoselective multi-enzymatic aminohydroxylation of β-methylstyrene using dioxygen, ammonia and formate
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We report an enzymatic route for the formal regio- and stereoselective aminohydroxylation of β-methylstyrene that consumes only dioxygen, ammonia and formate; carbonate is the by-product. The biocascade entails highly selective epoxidation, hydrolysis and hydrogen-borrowing alcohol amination. Thus, β-methylstyrene was converted into 1R,2R and 1S,2R-phenylpropanolamine in 59-63% isolated yields, and up to >99.5 : 0.5 dr and er.
- Corrado, Maria L.,Knaus, Tanja,Mutti, Francesco G.
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supporting information
p. 6246 - 6251
(2019/12/03)
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- Synthesis of organoaluminum chalcogenides and their applications in Lewis acid catalysis
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Two chalcogenide bridged bi-aluminum compounds [LAl(NMe3)(μ-S)Al(NMe3)L] (1) and [LAl(NMe3)(μ-Se)Al(NMe3)L] (2) were synthesized by reacting LAlH(NMe3) (L = 4-methylbenzylidene-o-aminothiophenol) with
- Ding, Yi,Ma, Xiaoli,Liu, Yashuai,Liu, Wenqing,Ni, Congjian,Yan, Ben,Yan, Li,Yang, Zhi
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- MAGNETIC NANOPARTICLE-IMMOBILIZED HYDROGENCARBONATE IMIDAZOLIUM
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PROBLEM TO BE SOLVED: To provide a novel magnetic nanoparticle-immobilized hydrogencarbonate imidazolium used for the silylcyanation of a carbonyl compound as a magnetic nanoparticle-immobilized catalyst. SOLUTION: A magnetic nanoparticle-immobilized hydr
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Paragraph 0042; 0043
(2018/02/24)
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- Low-valent magnesium(i)-catalyzed cyanosilylation of ketones
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The magnesium(i) complex [(XylNacnac)Mg]2 was employed as a highly efficient catalyst for the cyanosilylation of a variety of ketones with trimethylsilyl cyanide under mild conditions. In contrast to the traditional stoichiometric us
- Wang, Weifan,Luo, Man,Li, Jia,Pullarkat, Sumod A.,Ma, Mengtao
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supporting information
p. 3042 - 3044
(2018/03/28)
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- Method for aldehyde cyanosilylation reaction under conditions of no catalyst or solvent
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The invention discloses a method for an aldehyde cyanosilylation reaction under conditions of no catalyst or solvent. In a glove box, aldehyde and trimethylsilyl cyanide are sequentially added to a nuclear magnetic resonance tube, then, the glove box is m
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Paragraph 0049; 0050; 0051
(2018/11/22)
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- Preparation method of cyanalcohol silyl ether compound
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The invention discloses a preparation method of a cyanalcohol silyl ether compound. The preparation method comprises usage of a catalyst, the catalyst is a tridentate forceps-shaped ligand-stabilizedmagnesium lithium bimetallic compound. According to the
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Paragraph 0044; 0045; 0046
(2019/01/06)
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- Hydroboration, Cyanosilylation, and Sequential Cyanosilylation and Hydroboration of Carbonyl Compounds in the Presence of a TiIV Amido Complex as an Efficient Catalyst
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Catalytic hydroboration and cyanosilylation of a wide range of aldehydes and ketones, with pinacolborane (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) and trimethylsilyl cyanide, respectively, in the presence of titanium(IV) complexes [κ2-{(C5
- Harinath, Adimulam,Bhattcharjee, Jayeeta,Gorantla, Koteswar Rao,Mallik, Bhabani S.,Panda, Tarun K.
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supporting information
p. 3180 - 3192
(2018/07/06)
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- Hydrazone-based covalent organic frameworks for Lewis acid catalysis
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Hydrazone-based covalent organic frameworks (COFs) are rich in functional groups but have very limited variety and applications. Herein, two hydroxy-rich hydrazone-based COFs are synthesized in pure water and postsynthetically incorporated with CoII, exhibiting Lewis acid catalytic activity towards cyanosilylation of various aldehydes with size selectivity.
- Kundu, Tanay,Wang, Jian,Cheng, Youdong,Du, Yonghua,Qian, Yuhong,Liu, Guoliang,Zhao, Dan
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supporting information
p. 13824 - 13829
(2018/10/20)
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- Efficient and selective aldehyde cyanosilylation catalyzed by Mg-Li bimetallic complex
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A NCN-pincer ligand-based Mg-Li bimetallic complex [NCN-MgBr2][Li(THF)4] 1 has been employed as an efficient catalyst for cyanosilylation of a wide range of aldehydes with trimethylsilyl cyanide (TMSCN) at room temperature in CDClsu
- Li, Jia,Yu, Ting,Luo, Man,Xiao, Qian,Yao, Weiwei,Xu, Li,Ma, Mengtao
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- A bi-metallic MOF catalyst via sensitive detection & adsorption of Fe3+ ions for size-selective reaction prompting
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A cadmium(ii)-based MOF, Cd-MDIP, was successfully prepared by hydrothermal reaction between the tetra-carboxylic ligand 5,5′-methylenebisophthalic acid (H4MDIP) and cadmium perchlorate. The X-ray crystal structure analysis showed that there ar
- Li, Yang,Chang, Ziling,Huang, Fangmin,Wu, Pengyan,Chu, Huacong,Wang, Jian
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p. 9267 - 9273
(2018/07/29)
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- Synthesis of [LAl(μ-S)2AlL] (L?=?HC(CMeNAr)2, Ar?=?2,6-Et2C6H3) with the insertion of sulfur into the Al–H bonds of LAlH2 and its application in catalysis
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Two aluminum complexes [LAl(μ-S)2AlL] (1) and [LAl(SeH)2] (2) were synthesized in good yield by reacting one equivalent of LAlH2 (L?=?HC(CMeNAr)2, Ar?=?2,6-Et2C6H3) with one equivalent of S and with two equivalents of Se without any catalysts, respectively. Complexes 1 and 2 have been characterized by 1H and 13C NMR, elemental analyses, and single crystal X-ray structural analysis. Furthermore, the good catalytic activity of 1 as bimetallic Lewis acid catalyst for the addition reaction of TMSCN to aldehydes and aldimine condensation reactions, respectively, were investigated.
- Zhong, Mingdong,Liu, Ying,Liu, Xin,Ma, Xiaoli,Yang, Zhi
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supporting information
p. 182 - 185
(2017/05/24)
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- A cationic aluminium complex: An efficient mononuclear main-group catalyst for the cyanosilylation of carbonyl compounds
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A structurally characterized cationic aluminium complex [(AT)Al(DMAP)]+[OTf]- (3) stabilized through a relatively nonbulky aminotroponate (AT) ligand is reported (DMAP = 4-(dimethylamino)pyridine). This compound was found to work as
- Sharma, Mahendra Kumar,Sinhababu, Soumen,Mukherjee, Goutam,Rajaraman, Gopalan,Nagendran, Selvarajan
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supporting information
p. 7672 - 7676
(2017/07/11)
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- Synthesis of magnetically recoverable imidazolium hydrogen carbonate and its application as an N-heterocyclic carbene catalyst to cyanosilylation of aldehydes and ketones
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We prepared a magnetically recoverable imidazolium hydrogen carbonate by immobilizing an imidazolium hydrogen carbonate on magnetite and applied it as an N-heterocyclic carbene catalyst to the cyanosilylation of aldehydes and ketones. By employing the magnetite-supported imidazolium hydrogen carbonate as a catalyst, the cyanosilylation proceeded at 60?°C to provide the corresponding trimethylsilylated cyanohydrin in a fair chemical yield. Moreover, after the reaction, the magnetic catalyst was readily recovered by use of an external magnet and could be reused up to five times.
- Fujii, Akira,Choi, Jun-Chul,Fujita, Ken-ichi
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supporting information
p. 1515 - 1518
(2017/03/24)
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- Dimeric alumatranes as catalysts for trimethylsilylcyanation reaction
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The solid-state structures of dimeric alumatranes with three five-membered rings chelated by [(OCMe2CH2)nN(CH2CH2O)3-n]3- (n = 1, L1; n = 2, L2; n = 3, L3), which vary by the num
- Kim, Yoseph,Lee, Kang Mun,Kim, So Han,Moon, Jung Hee,Kim, Youngjo
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p. 48151 - 48160
(2017/11/03)
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- Lewis Acid Mediated Nazarov Cyclization as a Convergent and Enantioselective Entry to C-nor-D-homo-Steroids
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A straightforward synthesis of C-nor-D-homo steroids starting from (+)-Wieland–Miescher ketone is reported. This convergent synthetic strategy utilizes a?scalable diastereoselective Nazarov cyclization of functionalized chiral aryl vinyl ketones, allowing for further functionalization. The ability to conduct this key transformation on a multi-gram scale paves the way for the synthesis of a variety of completely new C-nor-D-homo steroids, without the need of a classic steran steroid rearrangement or achiral linear reaction sequences.
- Krieger, Johannes,Smeilus, Toni,Schackow, Oliver,Giannis, Athanassios
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supporting information
p. 5000 - 5004
(2017/04/18)
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- Synchronizing Substrate Activation Rates in Multicomponent Reactions with Metal-Organic Framework Catalysts
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A study on the influence of the cation coordination number, number of Lewis acid centers, concurrent existence of Lewis base sites, and structure topology on the catalytic activity of six new indium MOFs, has been carried out for multicomponent reactions (MCRs). The new indium polymeric frameworks, namely [In8(OH)6(popha)6(H2O)4]·3 H2O (InPF-16), [In(popha)(2,2′-bipy)]·3 H2O (InPF-17), [In3(OH)3(popha)2(4,4′-bipy)]·4 H2O (InPF-18), [In2(popha)2(4,4′-bipy)2]·3 H2O (InPF-19), [In(OH)(Hpopha)]·0.5 (1,7-phen) (InPF-20), and [In(popha)(1,10-phen)]·4 H2O (InPF-21) (InPF=indium polymeric framework, H3popha=5-(4-carboxy-2-nitrophenoxy)isophthalic acid, phen=phenanthroline, bipy=bipyridine), have been hydrothermally obtained by using both conventional heating (CH) and microwave (MW) procedures. These indium frameworks show efficient Lewis acid behavior for the solvent-free cyanosilylation of carbonyl compounds, the one pot Passerini 3-component (P-3CR) and the Ugi 4-component (U-4CR) reactions. In addition, InPF-17 was found to be a highly reactive, recyclable, and environmentally benign catalyst, which allows the efficient synthesis of α-aminoacyl amides. The relationship between the Lewis base/acid active site and the catalytic performance is explained by the 2D seven-coordinated indium framework of the catalyst InPF-17. This study is an attempt to highlight the main structural and synthetic factors that have to be taken into account when planning a new, effective MOF-based heterogeneous catalyst for multicomponent reactions.
- Aguirre-Díaz, Lina María,Iglesias, Marta,Snejko, Natalia,Gutiérrez-Puebla, Enrique,Monge, M. ángeles
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p. 6654 - 6665
(2016/05/09)
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- TBD-catalyzed cyanosilylation of aldehydes and ketones
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This study examines the catalytic efficacy of 1,5,7-triazabicyclo[4,4,0]dec-5-ene (TBD) in the cyanosilylation of aldehydes and ketones. In an aldehyde reaction, the corresponding products were obtained at high yield using minimal TBD (0.01 mol%). TBD was
- Matsukawa,Kimura
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p. 1947 - 1952
(2016/11/25)
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- Tunable catalytic activity of solid solution metal-organic frameworks in one-pot multicomponent reactions
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The aim of this research is to establish how metal-organic frameworks (MOFs) composed of more than one metal in equivalent crystallographic sites (solid solution MOFs) exhibit catalytic activity, which is tunable by virtue of the metal ions ratio. New MOF
- Aguirre-Díaz, Lina María,Gándara, Felipe,Iglesias, Marta,Snejko, Natalia,Gutiérrez-Puebla, Enrique,Monge, M. ángeles
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supporting information
p. 6132 - 6135
(2015/06/02)
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- Lanthanide metal-organic frameworks containing a novel flexible ligand for luminescence sensing of small organic molecules and selective adsorption
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Five lanthanide metal-organic frameworks, [Ln(L)(H2O)(NMP)]·1.5H2O (Ln = Ce (1), Pr (2); H3L = 1,3,5-tris(4-carboxyphenyl-1-ylmethyl)-2,4,6-trimethylbenzene), and [Ln2(L)2(H2O)3]
- Wang, Xiaoqing,Zhang, Liangliang,Yang, Jie,Liu, Fuling,Dai, Fangna,Wang, Rongming,Sun, Daofeng
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p. 12777 - 12785
(2015/06/25)
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- Solvent-free heterogeneous catalysis for cyanosilylation in a dynamic cobalt-MOF
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The butterfly-like tetranuclear cobalt cluster based 3D MOF [Me2NH2][Co2(bptc)(μ3-OH)(H2O)2] (1) underwent a reversible thermally triggered single-crystal-to-single-crystal transformation v
- Cui, Xin,Xu, Mei-Chen,Zhang, Ling-Juan,Yao, Ru-Xin,Zhang, Xian-Ming
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supporting information
p. 12711 - 12716
(2015/07/15)
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- Different acidity and additive effects of zirconium metal-organic frameworks as catalysts for cyanosilylation
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The Zr(iv) metal-organic framework with 1,4-benzenedicarboxylate (UiO-66) in different forms was studied as a solid catalyst for carbonyl cyanosilylation. The anhydrous material (UiO-66-A) obtained after calcination has open Lewis-acid sites and acts as a heterogeneous and size selective catalyst for the reaction of aldehydes and trimethylsilylcyanide (TMSCN). Notably, it was found that the as-synthesized hydrous form (UiO-66-H) shows comparable activity to UiO-66-A, so UiO-66 can be used as a catalyst for cyanosilylation with no need of high-temperature activation. With a number of intentionally designed control experiments, we demonstrated that the acetic acid enclosed in UiO-66-H during synthesis serves as a Bronsted acid to promote the reaction, though acetic acid is inactive by itself. The different acidity between UiO-66-H and UiO-66-A was confirmed by using the isomerization of α-pinene oxide as a probe reaction. Both UiO-66-H and UiO-66-A are recyclable without significant degradation in framework integrity and catalytic activity. In addition, it was unexpectedly found that pyridine, which is inactive alone, acts as co-catalyst, rather than a Lewis acid poison, to dramatically accelerate the catalytic reaction over UiO-66-H or UiO-66-A. A synergistic mechanism was suggested, in which the Lewis or Bronsted acid activates the aldehyde substrate while pyridine acts as a Lewis base to activate TMSCN.
- Xi, Fu-Gui,Yang, Yang,Liu, Hui,Yao, Hong-Fei,Gao, En-Qing
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p. 79216 - 79223
(2015/10/05)
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- A dual-functional Cd(II)-organic-framework demonstrating selective sensing of Zn2+ and Fe3+ ions exclusively and size-selective catalysis towards cyanosilylation
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A dual-functional complex with the formula Cd2(L)(DMF)2(H2O)2 (L = 2,3′,5,5′-biphenyl tetracarboxylic acid) has been successfully synthesized under solvothermal conditions and characterized by thermogravimetric
- Zhang, Xiao-Nan,Liu, Lin,Han, Zheng-Bo,Gao, Ming-Liang,Yuan, Da-Qiang
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p. 10119 - 10124
(2015/02/05)
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- CPO-27-M as heterogeneous catalysts for aldehyde cyanosilylation and styrene oxidation
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A series of isostructural 3D metal-organic frameworks of 2,5-dihydroxyterephthalate with different metal ions, CPO-27-M (or MOF-74-M, M = Co, Mg, Mn, Ni and Zn), have been studied as catalysts for cyanosilylation of aldehydes with trimethylsilylcyanide an
- Yao, Hong-Fei,Yang, Yang,Liu, Hui,Xi, Fu-Gui,Gao, En-Qing
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- Tri-lacunary polyoxometalates of Na8H[PW9O 34] as heterogeneous Lewis base catalysts for Knoevenagel condensation, cyanosilylation and the synthesis of benzoxazole derivatives
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We reported for the first time the development of tri-lacunary polyoxometalates (POMs) of Na8H[A-PW9O34] ·7H2O and Na8H[B-PW9O 34]·19H2O (Na-A-PW9 and Na-B-PW 9) as highly selective and efficient heterogeneous Lewis base catalysts for Knoevenagel condensation, cyanosilylation of various aldehydes and ketones and the synthesis of benzoxazole derivatives at 25 C under mild conditions. Since both Na-A-PW9 and Na-B-PW9 display no characteristic porosity, it is proposed that the catalytic reactions proceed not only on the surface and interface, but also in the bulk phase. The catalysts can be easily recovered and reused for at least six times without obvious decrease of catalytic activities and the structures of the catalysts remain unchanged after recycling. The easy preparation, high efficiency, reusability of the heterogeneous catalysts of Na-A-PW9 and Na-B-PW9 exhibit great potential for further application.
- Zhao, Shen,Chen, Yang,Song, Yu-Fei
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p. 140 - 146
(2014/03/21)
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