Zirconium-Based Catalysts in Organic Synthesis

Peng, Lifen; Zhao, Yanting; Yang, Tianbao; Zhou, Tong; Tang, Zilong; Orita, Akihiro; Qiu, Renhua

doi:10.1007/s41061-022-00396-4

Cited by 13 publications

(9 citation statements)

References 179 publications

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“…These materials also show changes in the position of the unit cell, indicating the formation of bimetallic clusters with interesting redox properties. [ 94 ] The alloying of Cu with Pd results in the formation of CuO x species with a size of 20 nm and PdCu species with smaller sizes. The diffraction patterns of the bimetallic PdCu species reveal their presence at 2 θ = 32, 35°, 51°, and 54°, with crystallite sizes ranging from 4 to 10 nm.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Vinyl Acetate Monomer Over PdCu Alloys: The Role of Surface Oxygenation in the Reaction Path

Gonzalez Caranton,

Schmal,

Checca Huaman

et al. 2023

Macro Reaction Engineering

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This work uses sol–gel and sonochemical methods to prepare bimetallic PdCu catalysts supported on modified ZrO2 with Ti and Al. The catalysts are tested for vinyl acetate synthesis from ethylene, acetic acid, and oxygen, varying the reaction temperature for two catalysts prepared, which show higher activity. Catalysts characterization results show bimetallic species and distort alloys with a dispersed distribution of active metal onto the support. The in situ reaction by DRIFT‐MS identifies the surface formation of main intermediates like palladium acetate monomers and mono and bidentate intermediates, associated to vinyl acetate formation, like vinyl hydrogenated species over PdCu. Finally, this behavior will be attributed to the bimetallic distortions of PdCu samples, provided by interaction effects between PdCu and supports, indicating a more exposition of PdCu species suitable for the reaction, according to high‐resolution transmission microscopy electron microscopy results for PdCu/ZrTi sample. Thus, this sample exhibits a minimal formation of sub‐products and catalytic stability for 18 hh. These results evidence the participation of hydroxyls and oxygen vacancies of the catalyst in the catalytic reaction measured in situ, monitoring the products formed at the reactor outlet. Finally, it is proposed a reaction pathway as a function of reaction conditions.

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Section: Resultsmentioning

confidence: 99%

Synthesis of Vinyl Acetate Monomer Over PdCu Alloys: The Role of Surface Oxygenation in the Reaction Path

Gonzalez Caranton,

Schmal,

Checca Huaman

et al. 2023

Macro Reaction Engineering

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“…Zirconium is employed both catalytically and as a stoichiometric reagent in organic synthesis, as recently reviewed by Qiu and co-workers. 13 These transformations provide inspiration for new and improved catalysis that may be accessible by employing multidentate ligands capable of supporting reactive, electrophilic metal centers with accessible coordination sites. We anticipate that the continuous exploration of these factors that influence reactivity will contribute to the expansion of early transition-metal catalysis.…”

Section: Summary and Final Remarks For Sectionmentioning

confidence: 99%

“…While these challenges remain, functionalization of simple petrochemical feedstocks to access value-added small-molecule building blocks suitable for further transformations can be effectively promoted by these metals. Zirconium is employed both catalytically and as a stoichiometric reagent in organic synthesis, as recently reviewed by Qiu and co-workers . These transformations provide inspiration for new and improved catalysis that may be accessible by employing multidentate ligands capable of supporting reactive, electrophilic metal centers with accessible coordination sites.…”

Section: Summary and Final Remarks For Sectionmentioning

confidence: 99%

“…Thus, the design of robust alternative monoanionic ligands has been key for the development of reactions catalyzed by group 4 elements, including zirconium. 13 The rich reactivity of titanium 5 can be attributed, at least in part, to the availability of several oxidation states, which have been exploited in catalytic transformations such as the Kulinkovich 14,15 and Pauson−Khand 16−18 reactions. 19,20 In contrast, low-valent zirconium complexes are far less common, 4 and while they have been employed in stoichiometric transformations for organic synthesis, 6 their catalytic application remains unexplored.…”

Section: Introductionmentioning

confidence: 99%

“…While the electron-rich cyclopentadienyl-derived ligands provide stabilization for group 4 complexes in high oxidation states, they also diminish their catalytic activity by decreasing electrophilicity and limiting steric accessibility at the metal center. Thus, the design of robust alternative monoanionic ligands has been key for the development of reactions catalyzed by group 4 elements, including zirconium …”

Section: Introductionmentioning

confidence: 99%

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From Stoichiometric to Catalytic E–H Functionalization by Non-Metallocene Zirconium Complexes─Recent Advances and Mechanistic Insights

Bahena

Schafer

2022

ACS Catal.

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The chemistry of group 4 elements has historically been dominated by the use of metallocene complexes in stoichiometric transformations. While this area continues to be widely explored, the development of non-cyclopentadienyl-based ligands has substantially contributed to the increase in applicability of group 4 metals in catalysis during the last 15 years. In addition to their application in polymerization catalysis, zirconium complexes supported by nitrogen-based anionic ligands have been useful as catalysts for a variety of E–H functionalization reactions. Two particular zirconium systems, (1) bis(ureate)-supported zirconium complexes reported by the Schafer group and (2) tripodal triamidoamine-supported zirconium complexes employed by the Waterman group, promote a variety of E–E′ bond-forming catalytic processes upon E/E′–H activation. The former system has been exploited for catalytic hydroamination, hydroaminoalkylation, and hydroalkynylation (alkyne dimerization) reactions, and the latter system has been used in hydrophosphination and dehydrocoupling reactions. This Perspective focuses on the bountiful reactivity of these catalytic systems with an emphasis on mechanistic insights of these transformations gained from a combination of kinetic analyses, isolation of reaction intermediates, stoichiometric reactivity studies, and computational calculations. The insights generated from this approach have revealed a series of features that enable catalytic E–E′ bond formation and that can contribute to guided efforts in early transition-metal ligand design. For the zirconium bis(ureate) system, the expanded coordination sphere promoted by the multidentate ligand facilitates the coordination of neutral amine donors that are essential for realizing innersphere E–H bond formation in hydrofunctionalization catalysis. For the triamidoamine-supported zirconium complexes, the noninnocent tripodal ligand mediates E–H bond formation/activation during catalysis. For both zirconium systems, the highly ionic nature of the chelating ligands has been shown to induce significant polarization of reactive Zr–E bonds (E = N, C, P). This bond polarization translates into exceptionally reactive Zr–E bonds, akin to those of rare earth metals, enabling σ-bond insertion reactions for E–E′ bond formation. The goal of this Perspective is to highlight examples where compelling evidence has been gathered demonstrating ligand design effects to promote zirconium catalysis. Lessons learned from the featured zirconium systems aim to highlight ligand design features that will advance new directions in early transition-metal catalysis.

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Magnetic biochar‐supported ZrO₂ as an efficient catalyst for one‐pot synthesis of 1′,4′‐dihydro‐3H,3′H‐spiro[furo[3,4‐b]quinoline‐9,2′‐quinoxaline]‐1,3′(4H)‐diones

Zhang

Dong

et al. 2022

Applied Organom Chemis

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A novel ZrO2 supported on a magnetic biochar material (CoFe2O4/BC‐ZrO2) was synthesized using a relatively simple route. The prepared CoFe2O4/BC‐ZrO2 was characterized by X‐ray diffraction (XRD), Fourier transform infrared (FT‐IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy‐dispersed X‐ray (EDX) elemental analysis, N2 adsorption–desorption isotherm, thermogravimetric analysis (TGA), and magnetic properties. The CoFe2O4/BC‐ZrO2 showed high catalytic activity for the synthesis of spiro[furo[3,4‐b]quinoline via a one‐pot three‐component reaction of benzene‐1,2‐diamine, indoline‐2,3‐dione, and tetronic acid. The catalyst can be recovered by an external magnetic field and recycled at least five times without significantly reducing its activity.

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Zirconium-Based Catalysts in Organic Synthesis

Cited by 13 publications

References 179 publications

Synthesis of Vinyl Acetate Monomer Over PdCu Alloys: The Role of Surface Oxygenation in the Reaction Path

Synthesis of Vinyl Acetate Monomer Over PdCu Alloys: The Role of Surface Oxygenation in the Reaction Path

From Stoichiometric to Catalytic E–H Functionalization by Non-Metallocene Zirconium Complexes─Recent Advances and Mechanistic Insights

Magnetic biochar‐supported ZrO₂ as an efficient catalyst for one‐pot synthesis of 1′,4′‐dihydro‐3H,3′H‐spiro[furo[3,4‐b]quinoline‐9,2′‐quinoxaline]‐1,3′(4H)‐diones

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Zirconium-Based Catalysts in Organic Synthesis

Cited by 13 publications

References 179 publications

Synthesis of Vinyl Acetate Monomer Over PdCu Alloys: The Role of Surface Oxygenation in the Reaction Path

Synthesis of Vinyl Acetate Monomer Over PdCu Alloys: The Role of Surface Oxygenation in the Reaction Path

From Stoichiometric to Catalytic E–H Functionalization by Non-Metallocene Zirconium Complexes─Recent Advances and Mechanistic Insights

Magnetic biochar‐supported ZrO2 as an efficient catalyst for one‐pot synthesis of 1′,4′‐dihydro‐3H,3′H‐spiro[furo[3,4‐b]quinoline‐9,2′‐quinoxaline]‐1,3′(4H)‐diones

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Magnetic biochar‐supported ZrO₂ as an efficient catalyst for one‐pot synthesis of 1′,4′‐dihydro‐3H,3′H‐spiro[furo[3,4‐b]quinoline‐9,2′‐quinoxaline]‐1,3′(4H)‐diones