- A Practice of Reticular Chemistry: Construction of a Robust Mesoporous Palladium Metal-Organic Framework via Metal Metathesis
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Constructing stable palladium(II)-based metal-organic frameworks (MOFs) would unlock more opportunities for MOF chemistry, particularly toward applications in catalysis. However, their availability is limited by synthetic challenges due to the inertness of the Pd-ligand coordination bond, as well as the strong tendency of the Pd(II) source to be reduced under typical solvothermal conditions. Under the guidance of reticular chemistry, herein, we present the first example of an azolate Pd-MOF, BUT-33(Pd), obtained via a deuterated solvent-assisted metal metathesis. BUT-33(Pd) retains the underlying sodalite network and mesoporosity of the template BUT-33(Ni) and shows excellent chemical stability (resistance to an 8 M NaOH aqueous solution). With rich Pd(II) sites in the atomically precise distribution, it also demonstrates good performances as a heterogeneous Pd(II) catalyst in a wide application scope, including Suzuki/Heck coupling reactions and photocatalytic CO2 reduction to CH4. This work highlights a feasible approach to reticularly construct noble metal based MOFs via metal metathesis, in which various merits, including high chemical stability, large pores, and tunable functions, have been integrated for addressing challenging tasks.
- He, Tao,Kong, Xiang-Jing,Li, Jian-Rong,Lv, Xiu-Liang,Nie, Zuo-Ren,Si, Guang-Rui,Wang, Kecheng,Wu, Xue-Qian,Zhao, Chen,Zhou, Jian
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supporting information
p. 9901 - 9911
(2021/07/21)
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- Synthesis and characterization of 4-AMTT-Pd(II) complex over Fe3O4@SiO2 as supported nanocatalyst for Suzuki-Miyaura and Mizoroki-heck cross-coupling reactions in water
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Immobilization of Pd(II) nanoparticles on silica-coated modified magnetite particles has been readily achieved via a surface modification of Fe3O4 particles with 4-amino-5-methyl-4-H-1,2,4-triazole-3-thiol (4-AMTT) as a ligand. This magnetite nanocatalyst was characterized by various analyses such as FT-IR, SEM/EDX, ICP-AES, VSM, TEM, XRD, XPS and TGA. This nanocatalyst showed admirable catalytic activity for Suzuki-Miyaura and Mizoroki-Heck cross-coupling reactions under mild conditions in water, and could be simply separated by an outer magnet and reused for several times.
- Hajipour, Abdol R.,Kalantari Tarrari, Mina,Jajarmi, Saeideh
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- An expedient approach to enhance Mizoroki-Heck coupling reaction by infrared irradiation using palladacycle compounds
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An alternative and environmentally friendly strategy to promote the Mizoroki-Heck cross-coupling reaction by the use of infrared irradiation using palladacycles as precatalysts is reported. Coupling products are obtained in high yield and short reaction time. A comparison with the classical use of reflux conditions, and commercial sources of palladium complexes, shows the advantages of this new alternative for promoting coupling reactions.
- Ortega-Jimnez, Fernando,Domnguez-Villa, Francisco X.,Rosas-Snchez, Alfredo,Penieres-Carrillo, Guillermo,Lpez-Corts, Jos G.,Ortega-Alfaro, M. Carmen
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p. 556 - 560
(2015/08/04)
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- Infrared irradiation assisted both the synthesis of (Z)-(aminomethyl)(aryl)phenylhydrazones via the Mannich coupling reaction and their application to the palladium-catalyzed Heck reaction
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The Mannich coupling reaction between arylhydrazones, formaldehyde and a secondary amine to generate the (Z)-(aminomethyl)(aryl)phenylhydrazones 1a-h assisted by infrared irradiation (IR) under solvent-free conditions is herein reported, and the catalytic potential of compounds 1a-h in the palladium-catalyzed and IR-assisted Heck coupling reaction is also evaluated. Coupling products are obtained in high yields and short reaction times. We show the advantages of this new alternative to promote both Mannich and Heck coupling reactions.
- Ortega-Jiménez, Fernando,Penieres-Carrillo, José Guillermo,Lagunas-Rivera, Selene,López-Cortés, José G.,álvarez-Toledano, Cecilio,Ortega-Alfaro, M. Carmen
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p. 80911 - 80918
(2015/10/06)
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- 2-Ferrocenyl-2-thiazoline as a building block of novel phosphine-free ligands
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New 1,2-disubstituted ferrocenes [5(b-j), in which R = -SMe, -SPh, -SiPr, -SiMe3, -SePh, -SnBu3, -B(OH)2, -Me, -I] with a thiazoline ring in the ferrocene backbone using as key intermediate a ferrocenyl Fischer carbene complex were synthesized. The capability of the 2-thiazoline moiety as an ortho-directed metalation group was demonstrated by subsequent quenching of lithium intermediate with several electrophiles, proving to be an excellent method for synthesizing bidentate ligands. The catalytic scope of the [N,S] ligand 5b as the corresponding palladium complex 5b-PdCl 2 in a microwave-promoted Heck reaction was also tested. Results obtained showed better catalytic activity of 5b-PdCl2 compared to other catalytic systems based on a [N,S] ferrocenyl ligand. The Royal Society of Chemistry.
- Corona-Sánchez, Ricardo,Toscano, Rubén A.,Ortega-Alfaro, M. Carmen,Sandoval-Chávez, César,López-Cortés, José G.
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p. 11992 - 12004
(2013/09/02)
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