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Journal articles on the topic 'Organometallic catalysts'

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Author: Grafiati

Published: 4 June 2021

Last updated: 7 September 2023

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1

Leitner, Walter. "Recent advances in catalyst immobilization using supercritical carbon dioxide." Pure and Applied Chemistry 76, no. 3 (January 1, 2004): 635–44. http://dx.doi.org/10.1351/pac200476030635.

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Homogeneous organometallic catalysts have a great potential for the development of sustainable synthetic processes. There is, however, an urgent need for the development of new techniques to separate products and catalysts efficiently, allowing for recycling and reuse of the precious catalyst. The unique solvent properties of supercritical carbon dioxide offer new approaches for the immobilization of organometallic catalysts, many of which are suitable for efficient continuous-flow operation. Recent research in this field tries to combine the molecular nature of organometallic catalysts with the reaction-engineering aspect of multiphase catalysis.

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2

Bagul, Rahul S., and Narayanaswamy Jayaraman. "Multivalent dendritic catalysts in organometallic catalysis." Inorganica Chimica Acta 409 (January 2014): 34–52. http://dx.doi.org/10.1016/j.ica.2013.07.058.

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3

Welin, Eric R., Chip Le, Daniela M. Arias-Rotondo, James K. McCusker, and David W. C. MacMillan. "Photosensitized, energy transfer-mediated organometallic catalysis through electronically excited nickel(II)." Science 355, no. 6323 (January 26, 2017): 380–85. http://dx.doi.org/10.1126/science.aal2490.

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Transition metal catalysis has traditionally relied on organometallic complexes that can cycle through a series of ground-state oxidation levels to achieve a series of discrete yet fundamental fragment-coupling steps. The viability of excited-state organometallic catalysis via direct photoexcitation has been demonstrated. Although the utility of triplet sensitization by energy transfer has long been known as a powerful activation mode in organic photochemistry, it is surprising to recognize that photosensitization mechanisms to access excited-state organometallic catalysts have lagged far behind. Here, we demonstrate excited-state organometallic catalysis via such an activation pathway: Energy transfer from an iridium sensitizer produces an excited-state nickel complex that couples aryl halides with carboxylic acids. Detailed mechanistic studies confirm the role of photosensitization via energy transfer.

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4

Chadwick, F. Mark, Alasdair I. McKay, Antonio J. Martinez-Martinez, Nicholas H. Rees, Tobias Krämer, Stuart A. Macgregor, and Andrew S. Weller. "Solid-state molecular organometallic chemistry. Single-crystal to single-crystal reactivity and catalysis with light hydrocarbon substrates." Chemical Science 8, no. 9 (2017): 6014–29. http://dx.doi.org/10.1039/c7sc01491k.

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5

Carballares, Diego, Roberto Morellon-Sterling, and Roberto Fernandez-Lafuente. "Design of Artificial Enzymes Bearing Several Active Centers: New Trends, Opportunities and Problems." International Journal of Molecular Sciences 23, no. 10 (May 10, 2022): 5304. http://dx.doi.org/10.3390/ijms23105304.

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Harnessing enzymes which possess several catalytic activities is a topic where intense research has been carried out, mainly coupled with the development of cascade reactions. This review tries to cover the different possibilities to reach this goal: enzymes with promiscuous activities, fusion enzymes, enzymes + metal catalysts (including metal nanoparticles or site-directed attached organometallic catalyst), enzymes bearing non-canonical amino acids + metal catalysts, design of enzymes bearing a second biological but artificial active center (plurizymes) by coupling enzyme modelling and directed mutagenesis and plurizymes that have been site directed modified in both or in just one active center with an irreversible inhibitor attached to an organometallic catalyst. Some examples of cascade reactions catalyzed by the enzymes bearing several catalytic activities are also described. Finally, some foreseen problems of the use of these multi-activity enzymes are described (mainly related to the balance of the catalytic activities, necessary in many instances, or the different operational stabilities of the different catalytic activities). The design of new multi-activity enzymes (e.g., plurizymes or modified plurizymes) seems to be a topic with unarguable interest, as this may link biological and non-biological activities to establish new combo-catalysis routes.

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6

Pike, Sebastian D., and Andrew S. Weller. "Organometallic synthesis, reactivity and catalysis in the solid state using well-defined single-site species." Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences 373, no. 2037 (March 13, 2015): 20140187. http://dx.doi.org/10.1098/rsta.2014.0187.

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Acting as a bridge between the heterogeneous and homogeneous realms, the use of discrete, well-defined, solid-state organometallic complexes for synthesis and catalysis is a remarkably undeveloped field. Here, we present a review of this topic, focusing on describing the key transformations that can be observed at a transition-metal centre, as well as the use of well-defined organometallic complexes in the solid state as catalysts. There is a particular focus upon gas–solid reactivity/catalysis and single-crystal-to-single-crystal transformations.

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7

Thomas, Stephen P., and Jingying Peng. "Activation Strategies for Earth-Abundant Metal Catalysis." Synlett 31, no. 12 (April 6, 2020): 1140–46. http://dx.doi.org/10.1055/s-0039-1690873.

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The use of earth-abundant metal-catalysed organic transformations has increased significantly in recent years. Where low-oxidation-state catalysts are required, the in situ activation of metal(II/III) salts offers an operationally simple method to access these catalysts. Here we present the development of activation strategies from the use of reducing organometallic reagents to endogenous activation. Applications in alkene and alkyne hydrofunctionalisation reactions will be used to highlight the synthetic applications of the activation methods discussed.1 Introduction2 In situ Activation Using Organometallic Reagents3 In situ Activation Using Nonorganometallic Reagents4 ‘Activator-Free’ Systems5 Conclusions

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8

RODINA, TATYANA ANDREEVNA. "ORGANOMETALLIC CATALYSTS FOR ETHYLENE POLYMERIZATION." Messenger AmSU, no. 93 (2021): 92–96. http://dx.doi.org/10.22250/jasu.93.20.

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The use of organometallic catalysts in ethylene polymerization at low pressure is considered. A comparative characteristic of different generations of catalysts and their influence on the physical and mechanical properties of polymers is given.

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9

Anila, Sebastian, and Cherumuttathu H. Suresh. "Endo- and exohedral chloro-fulleride as η5 ligands: a DFT study on the first-row transition metal complexes." Physical Chemistry Chemical Physics 23, no. 5 (2021): 3646–55. http://dx.doi.org/10.1039/d0cp05612j.

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10

Semetey, Vincent, and Benoît Rhoné. "Base-Catalyzed Transcarbamoylation." Synlett 28, no. 15 (June 7, 2017): 2004–7. http://dx.doi.org/10.1055/s-0036-1588866.

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Inorganic bases such as NaH, KOt-Bu, NaOH, or KOH are efficient catalysts to promote the transcarbamoylation reaction between urethanes and a variety of primary and secondary alcohols under mild conditions. They constitute an alternative to organometallic catalysis and can be applied to aliphatic or aromatic urethanes.

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11

Bonardi, Aude-Héloise, Frédéric Dumur, Guillaume Noirbent, Jacques Lalevée, and Didier Gigmes. "Organometallic vs organic photoredox catalysts for photocuring reactions in the visible region." Beilstein Journal of Organic Chemistry 14 (December 12, 2018): 3025–46. http://dx.doi.org/10.3762/bjoc.14.282.

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Recent progresses achieved in terms of synthetic procedures allow now the access to polymers of well-defined composition, molecular weight and architecture. Thanks to these recent progresses in polymer engineering, the scope of applications of polymers is far wider than that of any other class of material, ranging from adhesives, coatings, packaging materials, inks, paints, optics, 3D printing, microelectronics or textiles. From a synthetic viewpoint, photoredox catalysis, originally developed for organic chemistry, has recently been applied to the polymer synthesis, constituting a major breakthrough in polymer chemistry. Thanks to the development of photoredox catalysts of polymerization, a drastic reduction of the amount of photoinitiators could be achieved, addressing the toxicity and the extractability issues; high performance initiating abilities are still obtained due to the catalytic approach which regenerates the catalyst. As it is a fast-growing field, this review will be mainly focused on an overview of the recent advances concerning the development of organic and organometallic photoredox catalysts for the photoreticulation of multifunctional monomers for a rapid and efficient access to 3D polymer networks.

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12

Campbell, Allea, Ziad Alsudairy, Chaochao Dun, Fazli Akram, Kayla Smith-Petty, Abrianna Ambus, Danielle Bingham, Tandabany Dinadayalane, Conrad Ingram, and Xinle Li. "Dioxin-Linked Covalent Organic Framework-Supported Palladium Complex for Rapid Room-Temperature Suzuki–Miyaura Coupling Reaction." Crystals 13, no. 8 (August 17, 2023): 1268. http://dx.doi.org/10.3390/cryst13081268.

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Covalent organic framework (COF)-supported palladium catalysts have garnered enormous attention for cross-coupling reactions. However, the limited linkage types in COF hosts and their suboptimal catalytic performance have hindered their widespread implementation. Herein, we present the first study immobilizing palladium acetate onto a dioxin-linked COF (Pd/COF-318) through a facile solution impregnation approach. By virtue of its permanent porosity, accessible Pd sites arranged in periodic skeletons, and framework robustness, the resultant Pd/COF-318 exhibits exceptionally high activity and broad substrate scope for the Suzuki–Miyaura coupling reaction between aryl bromides and arylboronic acids at room temperature within an hour, rendering it among the most effective Pd/COF catalysts for Suzuki–Miyaura coupling reactions to date. Moreover, Pd/COF-318 demonstrates excellent recyclability, retaining high activity over five cycles without significant deactivation. The leaching test confirms the heterogeneity of the catalyst. This work uncovers the vast potential of dioxin-linked COFs as catalyst supports for highly active, selective, and durable organometallic catalysis.

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13

Angermund, K., and C. Krüger. "Structural investigations of organometallic catalysts, catalyst precursors and ligands." Acta Crystallographica Section A Foundations of Crystallography 43, a1 (August 12, 1987): C70. http://dx.doi.org/10.1107/s0108767387083612.

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14

Rajkiewicz, Adam A., Anna Kajetanowicz, and Karol Grela. "Self-Supported Polymeric Ruthenium Complexes as Olefin Metathesis Catalysts in Synthesis of Heterocyclic Compounds." Catalysts 12, no. 10 (September 21, 2022): 1087. http://dx.doi.org/10.3390/catal12101087.

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New ruthenium olefin metathesis catalysts containing N-heterocyclic carbene (NHC) connected by a linker tether to a benzylidene ligand were studied. Such obtained self-chelated Hoveyda–Grubbs type complexes existed in the form of an organometallic polymer but could still catalyze olefin metathesis after being dissolved in an organic solvent. Although these polymeric catalysts exhibited a slightly lower activity compared to structurally related nonpolymeric catalysts, they were successfully used in a number of ring-closing metathesis reactions leading to a variety of heterocyclic compounds, including biologically and pharmacologically related analogues of cathepsin K inhibitor and sildenafil (Viagra™). In the last case, a good solubility of a polymeric catalyst in toluene allowed the separation of the product from the catalyst via simple filtration.

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15

Balcar, Hynek, and Jiří Čejka. "SBA-15 as a Support for Effective Olefin Metathesis Catalysts." Catalysts 9, no. 9 (September 2, 2019): 743. http://dx.doi.org/10.3390/catal9090743.

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Olefin metathesis is the catalytic transformation of olefinic substrates, finding a wide range of applications in organic synthesis. The mesoporous molecular sieve Santa Barbara Amorphous (SBA-15) has proven to be an excellent support for metathesis catalysts thanks to its regular mesoporous structure, high BET area, and large pore volume. A survey of catalysts consisting of (i) molybdenum and tungsten oxides on SBA-15, and (ii) molybdenum and ruthenium organometallic complexes (Schrock and Grubbs-type carbenes) on SBA-15 is provided together with their characterization and catalytic performance in various metathesis reactions. The comparison with catalysts based on other supports demonstrates the high quality of the mesoporous molecular sieve SBA-15 as an advanced catalyst support.

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16

Kumar, Sandeep, Brij Mohan, Zhiyu Tao, Hengzhi You, and Peng Ren. "Incorporation of homogeneous organometallic catalysts into metal–organic frameworks for advanced heterogenization: a review." Catalysis Science & Technology 11, no. 17 (2021): 5734–71. http://dx.doi.org/10.1039/d1cy00663k.

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The heterogenization of homogeneous organometallic catalysts by incorporation into MOFs using different strategies, MOF selection, OMC selection, and the use of hybrid heterogeneous catalysts OMC@MOFs in catalytic applications are summarized and discussed.

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17

Ivanchikova, Irina D., Olga V. Zalomaeva, Nataliya V. Maksimchuk, Olga A. Stonkus, Tatiana S. Glazneva, Yurii A. Chesalov, Alexander N. Shmakov, Matteo Guidotti, and Oxana A. Kholdeeva. "Alkene Epoxidation and Thioether Oxidation with Hydrogen Peroxide Catalyzed by Mesoporous Zirconium-Silicates." Catalysts 12, no. 7 (July 5, 2022): 742. http://dx.doi.org/10.3390/catal12070742.

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Mesoporous zirconium-silicates have been prepared using two different methodologies, evaporation-induced self-assembly and solventless organometallic precursor dry impregnation of commercial SiO2. The samples were characterized by elemental analysis, XRD, N2 adsorption, TEM, DRS UV–vis and Raman spectroscopic techniques. The catalytic performance of the Zr-Si catalysts was assessed in the epoxidation of three representative alkenes, cyclohexene, cyclooctene and caryophyllene, as well as in the oxidation of methyl phenyl sulfide using aqueous hydrogen peroxide as a green oxidant, with special attention drawn to the structure/activity relationship and catalyst stability issues. The key factors which affect substrate conversion and epoxide selectivity have been defined. The catalysts with larger contents of oligomeric ZrO2 species revealed higher activity. The nature of alkene and, in particular, its molecular hindrance is crucial, since the adsorption of the epoxide product is the main factor leading to fast catalyst deactivation. In fact, bulky epoxides do not show this effect. After optimization, the oxidation of caryophyllene gave endocyclic monoepoxide with 77% selectivity at 87% alkene conversion. Methyl phenyl sulfoxide afforded 37% of sulfoxide and 63% of sulfone at 57% sulfide conversion. The nature of catalysis was truly heterogeneous and no Zr leaching was observed.

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18

Rotundo, Laura, Alice Barbero, Carlo Nervi, and Roberto Gobetto. "CO2 Electroreduction on Carbon-Based Electrodes Functionalized with Molecular Organometallic Complexes—A Mini Review." Catalysts 12, no. 11 (November 16, 2022): 1448. http://dx.doi.org/10.3390/catal12111448.

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Heterogeneous electrochemical CO2 reduction has potential advantages with respect to the homogeneous counterpart due to the easier recovery of products and catalysts, the relatively small amounts of catalyst necessary for efficient electrolysis, the longer lifetime of the catalysts, and the elimination of solubility problems. Unfortunately, several disadvantages are also present, including the difficulty of designing the optimized and best-performing catalysts by the appropriate choice of the ligands as well as a larger heterogeneity in the nature of the catalytic site that introduces differences in the mechanistic pathway and in electrogenerated products. The advantages of homogeneous and heterogeneous systems can be preserved by anchoring intact organometallic molecules on the electrode surface with the aim of increasing the dispersion of active components at a molecular level and facilitating the electron transfer to the electrocatalyst. Electrode functionalization can be obtained by non-covalent or covalent interactions and by direct electropolymerization on the electrode surface. A critical overview covering the very recent literature on CO2 electroreduction by intact organometallic complexes attached to the electrode is summarized herein, and particular attention is given to their catalytic performances. We hope this mini review can provide new insights into the development of more efficient CO2 electrocatalysts for real-life applications.

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19

Copéret, Christophe, Zachariah J. Berkson, Ka Wing Chan, Jordan de Jesus Silva, Christopher P. Gordon, Margherita Pucino, and Pavel A. Zhizhko. "Olefin metathesis: what have we learned about homogeneous and heterogeneous catalysts from surface organometallic chemistry?" Chemical Science 12, no. 9 (2021): 3092–115. http://dx.doi.org/10.1039/d0sc06880b.

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20

Laga, Stephanie M., Tanya M. Townsend, Abby R. O'Connor, and James M. Mayer. "Cooperation of cerium oxide nanoparticles and soluble molecular catalysts for alcohol oxidation." Inorganic Chemistry Frontiers 7, no. 6 (2020): 1386–93. http://dx.doi.org/10.1039/c9qi01640f.

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21

Błachucki, Wojciech, Jakub Szlachetko, Yves Kayser, Jean-Claude Dousse, Joanna Hoszowska, Daniel L. A. Fernandes, and Jacinto Sá. "Study of the reactivity of silica supported tantalum catalysts with oxygen followed by in situ HEROS." Physical Chemistry Chemical Physics 17, no. 28 (2015): 18262–64. http://dx.doi.org/10.1039/c5cp02950c.

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22

Bora, Debashree, Firdaus Rahaman Gayen, and Biswajit Saha. "Ammonia from dinitrogen at ambient conditions by organometallic catalysts." RSC Advances 12, no. 52 (2022): 33567–83. http://dx.doi.org/10.1039/d2ra06156b.

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23

Zhang, Wen-Ying, Samya Banerjee, George M. Hughes, Hannah E. Bridgewater, Ji-Inn Song, Ben G. Breeze, Guy J. Clarkson, et al. "Ligand-centred redox activation of inert organoiridium anticancer catalysts." Chemical Science 11, no. 21 (2020): 5466–80. http://dx.doi.org/10.1039/d0sc00897d.

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24

Sau, Samaresh Chandra, Pradip Kumar Hota, Swadhin K. Mandal, Michele Soleilhavoup, and Guy Bertrand. "Stable abnormal N-heterocyclic carbenes and their applications." Chemical Society Reviews 49, no. 4 (2020): 1233–52. http://dx.doi.org/10.1039/c9cs00866g.

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25

Bok, Agnieszka, Joanna Guziałowska-Tic, and Wilhelm Jan Tic. "Effects of Catalysts on Emissions of Pollutants from Combustion Processes of Liquid Fuels." Civil And Environmental Engineering Reports 13, no. 2 (December 10, 2014): 5–17. http://dx.doi.org/10.2478/ceer-2014-0011.

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Abstract The dynamic growth of the use of non-renewable fuels for energy purposes results in demand for catalysts to improve their combustion process. The paper describes catalysts used mainly in the processes of combustion of motor fuels and fuel oils. These catalysts make it possible to raise the efficiency of oxidation processes simultanously reducing the emission of pollutants. The key to success is the selection of catalyst compounds that will reduce harmful emissions of combustion products into the atmosphere. Catalysts are introduced into the combustion zone in form of solutions miscible with fuel or with air supplied to the combustion process. The following compounds soluble in fuel are inclused in the composition of the described catalysts: organometallic complexes, manganese compounds, salts originated from organic acids, ferrocen and its derivatives and sodium chloride and magnesium chloride responsible for burning the soot (chlorides). The priority is to minimize emissions of volatile organic compounds, nitrogen oxides, sulphur oxides, and carbon monoxide, as well as particulate matter.

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26

Thomsen, Julianne M., Daria L. Huang, Robert H. Crabtree, and Gary W. Brudvig. "Iridium-based complexes for water oxidation." Dalton Transactions 44, no. 28 (2015): 12452–72. http://dx.doi.org/10.1039/c5dt00863h.

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27

Rangel-Rangel, Elizabeth, Ester Verde-Sesto, Antonia M. Rasero-Almansa, Marta Iglesias, and Félix Sánchez. "Porous aromatic frameworks (PAFs) as efficient supports for N-heterocyclic carbene catalysts." Catalysis Science & Technology 6, no. 15 (2016): 6037–45. http://dx.doi.org/10.1039/c6cy00597g.

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28

Astruc, D. "Organometallic chemistry at the nanoscale. Dendrimers for redox processes and catalysis." Pure and Applied Chemistry 75, no. 4 (January 1, 2003): 461–81. http://dx.doi.org/10.1351/pac200375040461.

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An overview of the metal-mediated synthesis and use of nanosized metallodendrimers is given with emphasis on electron-transfer processes (molecular batteries consisting in dendrimers decorated with a large number of equivalent redox-active centers) and catalytic reactions (electron-transfer-chain catalytic synthesis of dendrimers decorated with ruthenium carbonyl clusters, redox catalysis of nitrate and nitrite electroreduction in water by star-shape hexanuclear catalysts).

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29

Pappuru, Sreenath, Debashis Chakraborty, and Venkatachalam Ramkumar. "Nb and Ta benzotriazole or benzoxazole phenoxide complexes as catalysts for the ring-opening polymerization of glycidol to synthesize hyperbranched polyglycerols." Dalton Transactions 46, no. 47 (2017): 16640–54. http://dx.doi.org/10.1039/c7dt02839c.

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30

Liebeskind, Lanny S., Jiri Srogl, Cecile Savarin, and Concepcion Polanco. "Bioinspired organometallic chemistry." Pure and Applied Chemistry 74, no. 1 (January 1, 2002): 115–22. http://dx.doi.org/10.1351/pac200274010115.

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Given the stability of the bond between a mercaptide ligand and various redox-active metals, it is of interest that Nature has evolved significant metalloenzymatic processes that involve key interactions of sulfur-containing functionalities with metals such as Ni, Co, Cu, and Fe. From a chemical perspective, it is striking that these metals can function as robust biocatalysts in vivo, even though they are often "poisoned" as catalysts in vitro through formation of refractory metal thiolates. Insight into the nature of this chemical discrepancy is under study in order to open new procedures in synthetic organic and organometallic chemistry.

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31

Onishi, Naoya, and Yuichiro Himeda. "CO2 hydrogenation to methanol by organometallic catalysts." Chem Catalysis 2, no. 2 (February 2022): 242–52. http://dx.doi.org/10.1016/j.checat.2021.11.010.

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32

Patton, Duncan A., and Matthew E. Cremeens. "Organometallic catalysts for intramolecular hydroamination of alkenes." Review Journal of Chemistry 4, no. 1 (January 2014): 1–20. http://dx.doi.org/10.1134/s207997801304002x.

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33

LI, X., and Z. HOU. "Organometallic catalysts for copolymerization of cyclic olefins." Coordination Chemistry Reviews 252, no. 15-17 (August 2008): 1842–69. http://dx.doi.org/10.1016/j.ccr.2007.11.027.

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34

Durkee, D. A., H. B. Eitouni, E. D. Gomez, M. W. Ellsworth, A. T. Bell, and N. P. Balsara. "Catalysts from Self-Assembled Organometallic Block Copolymers." Advanced Materials 17, no. 16 (August 18, 2005): 2003–6. http://dx.doi.org/10.1002/adma.200500352.

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35

Rossi, Laura I., and Manuel I. Velasco. "Alternatives to free molecular halogens as chemoselective reactants: Catalysis of organic reactions with reusable complexes of halogen metal salts." Pure and Applied Chemistry 84, no. 3 (February 6, 2012): 819–26. http://dx.doi.org/10.1351/pac-con-11-07-13.

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Organometallic complexes of halogen metallic salts have been used as catalysts in different organic reactions, mainly the oxidation of organic compounds. Their use has not only allowed the reduction of the amounts of catalyst (since they can be reused) but also a lower generation of byproducts and wastes. The different reaction media developed through the research were analyzed by several green parameters, and the best results were obtained with complexes that have cyclodextrins as organic ligands. The proposed methodology is an alternative to use of molecular halogen as oxidant or catalyst when halogens are significant chemoselective reactants.

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36

Mialane, P., C. Mellot-Draznieks, P. Gairola, M. Duguet, Y. Benseghir, O. Oms, and A. Dolbecq. "Heterogenisation of polyoxometalates and other metal-based complexes in metal–organic frameworks: from synthesis to characterisation and applications in catalysis." Chemical Society Reviews 50, no. 10 (2021): 6152–220. http://dx.doi.org/10.1039/d0cs00323a.

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37

Ogo, Seiji, Tatsuya Ando, Le Tu Thi Minh, Yuki Mori, Takahiro Matsumoto, Takeshi Yatabe, Ki-Seok Yoon, Yukio Sato, Takashi Hibino, and Kenji Kaneko. "A NiRhS fuel cell catalyst – lessons from hydrogenase." Chemical Communications 56, no. 79 (2020): 11787–90. http://dx.doi.org/10.1039/d0cc04789a.

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38

Cerezo-Navarrete, Christian, Patricia Lara, and Luis M. Martínez-Prieto. "Organometallic Nanoparticles Ligated by NHCs: Synthesis, Surface Chemistry and Ligand Effects." Catalysts 10, no. 10 (October 3, 2020): 1144. http://dx.doi.org/10.3390/catal10101144.

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Over the last 20 years, the use of metallic nanoparticles (MNPs) in catalysis has awakened a great interest in the scientific community, mainly due to the many advantages of this kind of nanostructures in catalytic applications. MNPs exhibit the characteristic stability of heterogeneous catalysts, but with a higher active surface area than conventional metallic materials. However, despite their higher activity, MNPs present a wide variety of active sites, which makes it difficult to control their selectivity in catalytic processes. An efficient way to modulate the activity/selectivity of MNPs is the use of coordinating ligands, which transforms the MNP surface, subsequently modifying the nanoparticle catalytic properties. In relation to this, the use of N-heterocyclic carbenes (NHC) as stabilizing ligands has demonstrated to be an effective tool to modify the size, stability, solubility and catalytic reactivity of MNPs. Although NHC-stabilized MNPs can be prepared by different synthetic methods, this review is centered on those prepared by an organometallic approach. Here, an organometallic precursor is decomposed under H2 in the presence of non-stoichiometric amounts of the corresponding NHC-ligand. The resulting organometallic nanoparticles present a clean surface, which makes them perfect candidates for catalytic applications and surface studies. In short, this revision study emphasizes the great versatility of NHC ligands as MNP stabilizers, as well as their influence on catalysis.

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39

Li, Li Min, San Kui Xu, Xiao Dong Wang, Nan Nan Guo, Yun Lai Su, and Peng Zhang. "Preparation of CuO/γ-Al₂O₃ Catalysts by Impregnationin Supercritical CO₂." Advanced Materials Research 396-398 (November 2011): 1313–17. http://dx.doi.org/10.4028/www.scientific.net/amr.396-398.1313.

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CuO/γ-Al2O3 catalysts were prepared by supercritical CO2 (SC-CO2) impregnation method. The preparation was carried out in SC-CO2 with Cu(NO3)2 as precursor, methanol as assistant solvent, and γ-Al2O3 as support. The effects of impregnation parameters such as temperature and pressure of SC-CO2, impregnation time, ratio of precursor to support, and amount of assistant solvent on catalyst preparation were investigated. The as-prepared catalysts were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis and compared to that prepared by the conventional impregnation method. The SC-CO2 impregnation method provided higher adsorption rate, larger adsorption quantity, more homogeneous dispersion of precursor, and stronger interaction between precursor and support. The catalytic degradation of methylene blue (MB) was used as probe reaction to estimate the catalytic activity of two catalysts prepared by two methods. The catalyst prepared by SC-CO2 impregnation method exhibits significantly improved catalytic activity. These results show that the inorganic metallic reagents as precursor with assistant solvent can be used as an alternative for the organometallic precursors in SC-CO2 impregnation method.

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40

Crozier, P. A., and P. Claus. "Nano-characterization of Rh-Sn bimetallic catalysts." Proceedings, annual meeting, Electron Microscopy Society of America 54 (August 11, 1996): 224–25. http://dx.doi.org/10.1017/s0424820100163587.

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Bimetallic catalysts are of considerable importance because they possess both high activity and selectivity. Recently, there has been considerable interest in bimetallic catalysts produced by surface organometallic chemistry on metals. A detailed description of the structure and composition at the nanometer level is critical to fully understand the behavior of such catalysts. We have undertaken a study of the microstructure of Rh-Sn/SiO2 bimetallic hydrogenation catalysts.A Rh-Sn precursor was prepared by reacting tetrabutyltin with a silica supported Rh parent catalyst (1 %Rh/SiO2). The bimetallic catalysts were produced by thermal decomposition of the precursor in flowing hydrogen at 623 K. Five different catalysts were produced with a range of different Sn loadings from Rh(1%)/SiO2 to Rh(1%)-Sn(1.85%)/SiO2. The resulting bimetallic catalysts were able to selectively hydrogenate isolated and conjugated C=O functional groups. In situ XPS showed that the Sn and Rh were in the fully reduced state. Mossbauer spectroscopy studies confirmed that Sn was present in the zerovalent state indicating that no oxidized Sn was present. Preliminary IR data suggests that most of the Rh atoms are isolated from their neighbors (presumably by Sn).

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Genêt, Jean-Pierre, Sylvain Darses, and Véronique Michelet. "Organometallic catalysts in synthetic organic chemistry: From reactions in aqueous media to gold catalysis." Pure and Applied Chemistry 80, no. 5 (January 1, 2008): 831–44. http://dx.doi.org/10.1351/pac200880050831.

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Water has attracted significant attention as an alternative solvent for transition-metal-catalyzed reactions. The use of water as solvent allows simplified procedures for separation of the catalyst from the products and recycling of the catalyst. Water is an inexpensive reagent for the formation of oxygen-containing products such as alcohols. The use of water as a medium for promoting organometallic and organic reactions is also of great potential. This chapter will focus on old and recent developments in the design and applications of some catalytic reactions using aqueous-phase Pd, Rh, Pt, and Au complexes.

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42

Ball, Philip. "Single-atom catalysis: a new field that learns from tradition." National Science Review 5, no. 5 (April 26, 2018): 690–93. http://dx.doi.org/10.1093/nsr/nwy043.

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Abstract Much of industrial chemical processing (in the petrochemicals industry, for example), and a great deal of laboratory chemical synthesis, involves catalysts that both lower the energy barrier to reaction and may help steer a reaction along a particular path. Traditionally, catalysts have come in two classes: heterogeneous, typically meaning that the catalyst is an extended solid; and homogeneous, where the catalyst is a small molecule that shares a solvent with the reactants. In heterogeneous catalysis, the reaction generally takes place on a surface, involving molecules attached there by covalent bonds. Homogeneous catalysts are often organometallic compounds, in which a metal atom or small cluster of atoms supplies the active site for reaction. In recent years, these distinctions have become somewhat blurred thanks to the advent of single-atom catalysis, where the catalytic site consists of a single atom (as in many homogeneous catalysts) attached to or embedded in a surface. The emergence of this field might be regarded as the logical conclusion of the use of ‘supported metal clusters’—small metal particles of nanometer scale and below, containing perhaps hundreds, tens or just a few atoms. It has became clear that such clusters can sometimes provide greater product selectivity and activity than macro-sized particles or powders of the same metal, partly because the active sites might be atoms at particular locations (such as edges and corners) in the nanoscale particles. By reducing their scale down to the level of single atoms, one can optimize these properties. At the same time, the potential uniformity of the atoms’ environments makes such catalysts more amenable to rational design and modeling to understand mechanism. This field represents an appealing blend of fundamental chemistry and physics—from the quantum-mechanical level upwards—and applied research aimed at producing many of the products vital to society, such as fuels and materials. Researchers in China have been strongly active in this field in recent years (see, for example, refs [1–5]). Jean Marie Basset of the King Abdullah University of Science and Technology in Thuwal, Saudi Arabia, is one of the leading practitioners in the area, and National Science Review spoke to him about the development and prospects of the field.

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Halpern, Jack. "Organometallic chemistry at the threshold of a new millennium. Retrospect and prospect." Pure and Applied Chemistry 73, no. 2 (January 1, 2001): 209–20. http://dx.doi.org/10.1351/pac200173020209.

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The evolution of organometallic chemistry during the second half of the 20th century has transformed chemical science and technology to a degree and in ways that have rarely been matched throughout the history of chemistry. These include the discovery of radically new types of chemical compounds; novel structures and bonding modes; unprecedented reactivity patterns; unsuspected roles of organometallic chemistry in biology; powerful new synthetic methodologies; new materials; and whole new classes of catalysts and catalytic processes of extraordinary versatility and selectivity. The impact of these developments, which still are unfolding, has been truly revolutionary. Some milestones in this remarkable chapter of chemical history, as well as challenges and opportunities confronting organometallic chemistry today, will be examined.

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Leclercq, Loïc, and Andreea R. Schmitzer. "Assembly of Tunable Supramolecular Organometallic Catalysts with Cyclodextrins." Organometallics 29, no. 15 (August 9, 2010): 3442–49. http://dx.doi.org/10.1021/om1006215.

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Cheung, Fung Kei, Mark A. Graham, Franco Minissi, and Martin Wills. "“Ether-Linked” Organometallic Catalysts for Ketone Reduction Reactions." Organometallics 26, no. 22 (October 2007): 5346–51. http://dx.doi.org/10.1021/om700610y.

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Notestein, Justin M., Enrique Iglesia, and Alexander Katz. "Grafted Metallocalixarenes as Single-Site Surface Organometallic Catalysts." Journal of the American Chemical Society 126, no. 50 (December 2004): 16478–86. http://dx.doi.org/10.1021/ja0470259.

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Jespersen, Daniel, Brockton Keen, Jon I. Day, Anuradha Singh, Justin Briles, Duncan Mullins, and Jimmie D. Weaver. "Solubility of Iridium and Ruthenium Organometallic Photoredox Catalysts." Organic Process Research & Development 23, no. 5 (March 18, 2019): 1087–95. http://dx.doi.org/10.1021/acs.oprd.9b00041.

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KUHN, F., A. SANTOS, A. JOGALEKAR, F. PEDRO, P. RIGO, and W. BARATTA. "Highly selective organometallic ruthenium catalysts for aldehyde olefination." Journal of Catalysis 227, no. 1 (October 1, 2004): 253–56. http://dx.doi.org/10.1016/j.jcat.2004.07.011.

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Fu, Gregory C. "New applications of organometallic catalysts in organic chemistry." Pure and Applied Chemistry 74, no. 1 (January 1, 2002): 33–36. http://dx.doi.org/10.1351/pac200274010033.

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LENSIK, C., and N. B. MILESTONE. "ChemInform Abstract: Organometallic Molecular Catalysts, Small Molecule Machines." ChemInform 29, no. 13 (June 23, 2010): no. http://dx.doi.org/10.1002/chin.199813294.

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