Directing transition metal-based oxygen-functionalization catalysis

Tomboc, Gracita M.; Park, Yeji; Lee, Kwangyeol; Jin, Kyoungsuk

doi:10.1039/d1sc01272j

Cited by 9 publications

(13 citation statements)

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“…Isolable ethylene complexes are increasingly rare for heavier Ag and Au, − and the number of isostructural copper(I), silver(I), and gold(I) complexes of ethylene available for the study of group 11 trends are also limited in number. − That is notable considering the important roles played by coinage metals in several key applications involving ethylene. For example, copper(I)-catalyzed oxychlorination of ethylene, silver-catalyzed epoxidation of ethylene to ethylene oxide, , and gold-mediated 1,2-difunctionalization and cyclopropanation of ethylene are known. − The involvement of gold–ethylene complexes as a reagent in oxidative addition chemistry of aryl-iodides by Russel in 2018 and alkynylation of cyclopropenes in 2019 by Hashmi, utilizing cationic gold(I) ethylene complexes supported by 4,4′-difluoro-2,2′-bipyridine and 1,10-phenanthroline as catalysts have been reported. Furthermore, recently, our group demonstrated the utility of polyfluorinated pyrazolate and bis(pyrazolyl)borate-supported copper(I) complexes for the highly selective separation of ethylene from ethane. , Likewise, silver(I) complexes have found applications in ethylene separation .…”

Section: Introductionmentioning

confidence: 99%

Copper(I), Silver(I), and Gold(I) Ethylene Complexes of Fluorinated and Boron-Methylated Bis- and Tris(pyridyl)borate Chelators

et al. 2023

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Bis- and tris-pyridyl borate ligands containing pyridyl donor arms, a methylated boron cap, and a fluorine-lined coordination pocket have been prepared and utilized in coinage metal chemistry. The tris(pyridyl)borate ligand has been synthesized using a convenient boron source, [NBu4][MeBF3]. These N-based ligands permitted the isolation of group 11 metal–ethylene complexes [MeB(6-(CF3)Py)3]M(C2H4) and [Me2B(6-(CF3)Py)2]M(C2H4) (M = Cu, Ag, Au). The gold complexes display the largest coordination-induced upfield shifts of the ethylene 13C resonance relative to that of the free ethylene in their NMR spectra, while the silver complexes show the smallest shift. Solid-state structures of five of these metal–ethylene complexes as well as the related free ligands were established by X-ray crystallography. Surprisingly, all three [MeB(6-(CF3)Py)3]M(C2H4) adopt the rare κ2 coordination mode rather than the typical κ3 coordination mode of facial capping tridentate ligands. Computational analyses indicate that κ2 coordination mode is favored over the κ3-mode in these coinage metal–ethylene complexes and point to the effects CF3-substituents have on κ2/κ3-energy difference. The M–C and M–N bond distances of [MeB(6-(CF3)Py)3]M(C2H4) follow the trend expected based on covalent radii of M(I) ions. The calculated ethylene–M interaction energy of κ2-[MeB(6-(CF3)Py)3]M(C2H4) indicated that the gold(I) forms the strongest interaction with ethylene. A comparison to the related poly(pyrazolyl)borates is also presented.

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Section: Introductionmentioning

confidence: 99%

Copper(I), Silver(I), and Gold(I) Ethylene Complexes of Fluorinated and Boron-Methylated Bis- and Tris(pyridyl)borate Chelators

et al. 2023

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“…Another partial oxidation reaction sometimes assisted by electrocatalysts is the conversion of alcohols to aldehydes or ketones, for which metal complexes with Ru, ,, Rh, Ir, and Ni , have been used. It appears that in many cases selective oxidation is achievable thanks to the formation of specific peroxide and superoxide intermediates at the metal center, in oxygen reduction reaction (ORR) steps analogous to those seen in enzymatic catalysis (Figure ); − the electrogenerated superoxide species can function as a base, a nucleophile, an oxidant, a reductant, an electron transfer shuttle, or a free radicals …”

Section: Adsorbates As Co-catalysts or Catalyst Modifiersmentioning

confidence: 99%

Designing Sites in Heterogeneous Catalysis: Are We Reaching Selectivities Competitive With Those of Homogeneous Catalysts?

Zaera

2022

Chem. Rev.

167

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A critical review of different prominent nanotechnologies adapted to catalysis is provided, with focus on how they contribute to the improvement of selectivity in heterogeneous catalysis. Ways to modify catalytic sites range from the use of the reversible or irreversible adsorption of molecular modifiers to the immobilization or tethering of homogeneous catalysts and the development of well-defined catalytic sites on solid surfaces. The latter covers methods for the dispersion of single-atom sites within solid supports as well as the use of complex nanostructures, and it includes the post-modification of materials via processes such as silylation and atomic layer deposition. All these methodologies exhibit both advantages and limitations, but all offer new avenues for the design of catalysts for specific applications. Because of the high cost of most nanotechnologies and the fact that the resulting materials may exhibit limited thermal or chemical stability, they may be best aimed at improving the selective synthesis of high value-added chemicals, to be incorporated in organic synthesis schemes, but other applications are being explored as well to address problems in energy production, for instance, and to design greener chemical processes. The details of each of these approaches are discussed, and representative examples are provided. We conclude with some general remarks on the future of this field.

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“…Due to the ring strain and polarization of the C-O bonds in the 3MR, the epoxide group is highly reactive, making epoxides valuable chemical intermediates stretching from organic synthesis and catalysis [1][2][3][4][5], the design of polymers and materials, e.g., based on natural terpene epoxides [6] to their use as raw materials in various industries producing fine chemicals for pharmaceuticals, fragrances, food or other agricultural products [7][8][9][10][11][12][13][14][15][16]. Ethylene oxide and propylene oxide are among the highest volume products in our industry, with annual production rates of 15 and 3 Mt per year, respectively [1]. The major source of epoxide intermediates is the epoxidation of olefins [17][18][19][20][21][22].…”

Section: Introductionmentioning

confidence: 99%

“…There are different routes for the synthesis of epoxides, such as oxidation of alkenes [35] or the reaction of alkenes with peroxides [36,37] or often supported by catalysts [1,7]. The epoxidation of allyl alcohols with peroxides leads to important raw materials for the production of glycerol and is also used as a precursor to many specialized compounds, such as flame-resistant materials, drying oils and plasticizers [38].…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Details of the Sharpless Epoxidation of Allylic Alcohols—A Combined URVA and Local Mode Study

Freindorf

Kraka

2022

Catalysts

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In this work, we investigated the catalytic effects of a Sharpless dimeric titanium (IV)–tartrate–diester catalyst on the epoxidation of allylalcohol with methyl–hydroperoxide considering four different orientations of the reacting species coordinated at the titanium atom (reactions R1–R4) as well as a model for the non-catalyzed reaction (reaction R0). As major analysis tools, we applied the URVA (Unified Reaction Valley Approach) and LMA (Local Mode Analysis), both being based on vibrational spectroscopy and complemented by a QTAIM analysis of the electron density calculated at the DFT level of theory. The energetics of each reaction were recalculated at the DLPNO-CCSD(T) level of theory. The URVA curvature profiles identified the important chemical events of all five reactions as peroxide OO bond cleavage taking place before the TS (i.e., accounting for the energy barrier) and epoxide CO bond formation together with rehybridization of the carbon atoms of the targeted CC double bond after the TS. The energy decomposition into reaction phase contribution phases showed that the major effect of the catalyst is the weakening of the OO bond to be broken and replacement of OH bond breakage in the non-catalyzed reaction by an energetically more favorable TiO bond breakage. LMA performed at all stationary points rounded up the investigation (i) quantifying OO bond weakening of the oxidizing peroxide upon coordination at the metal atom, (ii) showing that a more synchronous formation of the new CO epoxide bonds correlates with smaller bond strength differences between these bonds, and (iii) elucidating the different roles of the three TiO bonds formed between catalyst and reactants and their interplay as orchestrated by the Sharpless catalyst. We hope that this article will inspire the computational community to use URVA complemented with LMA in the future as an efficient mechanistic tool for the optimization and fine-tuning of current Sharpless catalysts and for the design new of catalysts for epoxidation reactions.

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Directing transition metal-based oxygen-functionalization catalysis

Abstract: This review presents the recent progress of oxygen functionalization catalysis via non-electrochemical (conventional organic synthesis) and electrochemical routes.

Cited by 9 publications

References 197 publications

Copper(I), Silver(I), and Gold(I) Ethylene Complexes of Fluorinated and Boron-Methylated Bis- and Tris(pyridyl)borate Chelators

Copper(I), Silver(I), and Gold(I) Ethylene Complexes of Fluorinated and Boron-Methylated Bis- and Tris(pyridyl)borate Chelators

Designing Sites in Heterogeneous Catalysis: Are We Reaching Selectivities Competitive With Those of Homogeneous Catalysts?

Mechanistic Details of the Sharpless Epoxidation of Allylic Alcohols—A Combined URVA and Local Mode Study

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