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Organometallic Homogeneous Catalysis
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Organometallic Homogeneous Catalysis

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Catalytic Materials".

Deadline for manuscript submissions: closed (20 November 2023) | Viewed by 16230

Special Issue Editor

Prof. Dr. Francisco J. Fernández-Alvarez

E-Mail Website
Guest Editor
Departamento de Química Inorgánica-ISQCH, Universidad de Zaragoza, Zaragoza, Spain
Interests: transition-metal-based homogeneous catalysis and its application for the activation and transformation of small molecules, such as CO2, formic acid, ketones, aldehydes, alkynes, etc.

Special Issue Information

Dear Colleagues,

Organometallic homogeneous catalysts (OHCs), named in this way to differentiate them from organometallic supported catalysts, have become essential tools in organic synthesis, especially in the production of fine chemicals. One of the advantages of OHCs is their selectivity, which allows the formation of the desired products with high performance. This is due to their ability to promote the selective activation of C−E (where E = H or heteroatom) bonds and subsequent coupling reactions. There are several reasons behind the high performance of OHCs, among which the following stand out: i) the great variability of oxidation and coordination numbers that are found in transition metal complexes, ii) the ability of transition-metal-based catalysts to reversibly change between oxidation states and coordination numbers during a catalytic process, and iii) the fact that the performance of OHCs can be easily tuned by varying the electronic and/or steric properties of the active site (nature of the ligands). The use of OHCs has allowed the development of environmentally benign catalytic processes for obtaining polymers, allylic acetates, alcohols, aldehydes, ketones, and esters in good yields, with high stereoselectivity, and at an industrial scale by catalytic oxidation, hydroformylation, polymerization, metathesis, and a range of other transformative processes. Moreover, OHCs have been successfully employed at laboratory scale in CO2 reduction processes, selective dehydrogenation of formic acid, and nitrogen fixation processes, among others.

This Special Issue aims to show the state-of-the-art and future applications of OHCs and includes experimental and theoretical studies as well as revisions.

Keywords

  • homogeneous catalysis
  • sustainable chemistry
  • small molecule activation
  • CO2 valorization
  • hydrogenation
  • hydroformylation
  • hydroamination
  • hydrosilylation
  • carboxylation
  • polymerization

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Published Papers (6 papers)

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Research

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19 pages, 5424 KiB  
Article
Insights into the Mechanism, Regio-/Diastereoselectivities and Ligand Role of Nickel-Initiated [3+2] Cycloadditions between Vinylcyclopropane and N-Tosylbenzaldimine
by Weihua Mu, Lin Zhu, Shuya Xia, Xue Tan, Liangfei Duan, Guanghao Meng and Guo Liu
Catalysts 2024, 14(1), 82; https://doi.org/10.3390/catal14010082 - 18 Jan 2024
Viewed by 1321
Abstract
Density functional theory (DFT) was employed to explore the reaction mechanism, regio- and diastereoselectivities of nickel-initiated [3+2] cycloaddition between vinylcyclopropane (VCP) and N-tosylbenzaldimine assisted by phosphine ligands. Four different binding modes of the nickel center to VCP substrate were explored during the [...] Read more.
Density functional theory (DFT) was employed to explore the reaction mechanism, regio- and diastereoselectivities of nickel-initiated [3+2] cycloaddition between vinylcyclopropane (VCP) and N-tosylbenzaldimine assisted by phosphine ligands. Four different binding modes of the nickel center to VCP substrate were explored during the ring-opening of VCP, among which the C,C_anti and C,C_syn modes were verified to be the most accessible ones. Further explorations about four different phosphine ligand-assisted reactions based on the two most probable binding modes show that the difference in binding mode of bi- and monodentate phosphine ligands can vary the optimal reaction pathway, especially in the [3+2] cycloaddition process between the ring-opened intermediate and N-tosylbenzaldimine. The formation of C–C and C–N bonds between N-tosylbenzaldimine and the ring-opened intermediate through [3+2] cycloaddition is found to be stepwise, with the former acting as the rate-determining step (RDS) in most cases. Computed free energy barriers of RDS transition states on the optimal path I or II not only give out good predictions for reaction rates and half-lives, but also provide reasonable explanations for the major generation of cis-pyrrolidine. Noncovalent interaction analyses of key stationary points suggest the rate is influenced by both electronic effects and steric hindrance, while the diastereoselectivity is mainly controlled by electronic effects. Full article
(This article belongs to the Special Issue Organometallic Homogeneous Catalysis)
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16 pages, 8764 KiB  
Article
Ru/Pd Complex and Its Monometallic Fragments as Catalysts for Norbornene Polymerization via ROMP and Addition
by Thaís R. Cruz, Gustavo H. C. Masson, Kelly A. E. Amorim, Antonio E. H. Machado, Beatriz E. Goi and Valdemiro P. Carvalho-Jr.
Catalysts 2022, 12(10), 1111; https://doi.org/10.3390/catal12101111 - 26 Sep 2022
Cited by 1 | Viewed by 2055
Abstract
The [Ru(PPh3)2Cl-piperidine(4-aminomethyl)] complex (mono-Ru) was synthesized from [Ru(PPh3)3Cl2] and 4-(aminomethyl)piperidine, whereas the [(PPh3)PdCl(Shiff-pip)] complex (mono-Pd) was obtained by reacting [Pd(PPh3)2Cl2] with its respective Schiff base [...] Read more.
The [Ru(PPh3)2Cl-piperidine(4-aminomethyl)] complex (mono-Ru) was synthesized from [Ru(PPh3)3Cl2] and 4-(aminomethyl)piperidine, whereas the [(PPh3)PdCl(Shiff-pip)] complex (mono-Pd) was obtained by reacting [Pd(PPh3)2Cl2] with its respective Schiff base ligand, both at a 1:1 molar ratio. The heterobimetallic [RuCl2(PPh3)2](μ-Schiff)Pd(PPh3)Cl] complex (Ru/Pd) was synthesized via a one-pot, three-component reaction of mono-Ru, [(Pd(PPh3)2Cl2] and salicylaldehyde. All complexes were fully characterized by FTIR, UV-Vis, and NMR spectroscopy, as well as elemental analysis, MALDI-TOF mass spectrometry, cyclic voltammetry, and computational studies. Ru/Pd was able to polymerize norbornene (NBE) by two different mechanisms: ROMP and vinyl polymerization. The Ru fragment was active for ROMP of NBE, reaching yields of 68 and 31% for mono-Ru and Ru/Pd, respectively, when the [NBE]/[Ru] = 3000 molar ratio and 5 μL EDA addition were employed at 50 °C. The poly(norbornene) (polyNBE) obtained presented an order of magnitude of 104 g mol−1 and Ð values between 1.48 and 1.79. For the vinyl polymerization of NBE, the Pd fragment was active using MAO as a cocatalyst, reaching a yield of 47.0% for Ru/Pd and quantitative yields for mono-Pd when [Al]/[Pd] = 2500 and [NBE]/[Pd] = 20,000 molar ratios were employed, both at 60 °C. Full article
(This article belongs to the Special Issue Organometallic Homogeneous Catalysis)
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20 pages, 2050 KiB  
Article
Syntheses of Silylene-Bridged Thiophene-Fused Cyclopentadienyl ansa-Metallocene Complexes for Preparing High-Performance Supported Catalyst
by Sun Mi Jeong, Ju Yong Park, Yong Bin Hyun, Jun Won Baek, Hagjun Kim, Yeokwon Yoon, Sangchul Chung, Junseong Lee and Bun Yeoul Lee
Catalysts 2022, 12(3), 283; https://doi.org/10.3390/catal12030283 - 2 Mar 2022
Cited by 4 | Viewed by 2751
Abstract
We synthesized a series of Me2Si-bridged ansa-zirconocene complexes coordinated by thiophene-fused cyclopentadienyl and fluorenyl ligands (Me2Si(2-R1-3-R2-4,5-Me2C7S)(2,7-R32C13H6))ZrMe2 (R1 = Me or H, [...] Read more.
We synthesized a series of Me2Si-bridged ansa-zirconocene complexes coordinated by thiophene-fused cyclopentadienyl and fluorenyl ligands (Me2Si(2-R1-3-R2-4,5-Me2C7S)(2,7-R32C13H6))ZrMe2 (R1 = Me or H, R2 = H or Me, R3 = H, tBu, or Cl) for the subsequent preparation of supported catalysts. We determined that the fluorenyl ligand adopts an η3-binding mode in 9 (R1 = Me, R2 = H, R3 = H) by X-ray crystallography. Further, we synthesized a derivative 15 by substituting the fluorenyl ligand in 9 with a 2-methyl-4-(4-tert-butylphenyl)indenyl ligand, derivatives 20 and 23 by substituting the Me2Si bridge in 12 (R1 = Me, R2 = H, R3 = tBu) and 15 with a tBuO(CH2)6(Me)Si bridge, and the dinuclear congener 26 by connecting two complexes with a –(Me)Si(CH2)6Si(Me)– spacer. The silica-supported catalysts prepared using 12, 20, and 26 demonstrated up to two times higher productivity in ethylene/1-hexene copolymerization than that prepared with conventional (THI)ZrCl2 (21–26 vs. 12 kg-PE/g-(supported catalyst)), producing polymers with comparable molecular weight (Mw, 330–370 vs. 300 kDa), at a higher 1-hexene content (1.3 vs. 1.0 mol%) but a lower bulk density of polymer particles (0.35 vs. 0.42 g/mL). Full article
(This article belongs to the Special Issue Organometallic Homogeneous Catalysis)
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Review

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23 pages, 4563 KiB  
Review
Advances in Cross-Coupling Reactions Catalyzed by Aromatic Pincer Complexes Based on Earth-Abundant 3d Metals (Mn, Fe, Co, Ni, Cu)
by Jesús Antonio Cruz-Navarro, Arturo Sánchez-Mora, Juan S. Serrano-García, Andrés Amaya-Flórez, Raúl Colorado-Peralta, Viviana Reyes-Márquez and David Morales-Morales
Catalysts 2024, 14(1), 69; https://doi.org/10.3390/catal14010069 - 16 Jan 2024
Cited by 3 | Viewed by 2766
Abstract
The increase of noble-metal-free catalysis in organic chemistry is a trending topic in constant growth due to the price increase of noble metals and their scarce abundance. As a result, many earth-abundant transition-metal complexes containing nickel, iron, or cobalt have been successfully applied [...] Read more.
The increase of noble-metal-free catalysis in organic chemistry is a trending topic in constant growth due to the price increase of noble metals and their scarce abundance. As a result, many earth-abundant transition-metal complexes containing nickel, iron, or cobalt have been successfully applied in the homogeneous catalysis of a wide number of cross-coupling reactions, and the use of pincer complexes based on these earth-abundant metals was recently explored, affording interesting results. Thus, this review provides a general overview of earth-abundant 3D pincer complexes and their application during the last decade as catalysts in cross-coupling reactions such as Kumada–Corriu, Suzuki–Miyaura, Sonogashira, C–S cross-coupling, and C–N bond-forming reactions. Full article
(This article belongs to the Special Issue Organometallic Homogeneous Catalysis)
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36 pages, 9272 KiB  
Review
Heterobimetallic Complexes of Bi- or Polydentate N-Heterocyclic Carbene Ligands and Their Catalytic Properties
by Csilla Enikő Czégéni, Ferenc Joó, Ágnes Kathó and Gábor Papp
Catalysts 2023, 13(11), 1417; https://doi.org/10.3390/catal13111417 - 5 Nov 2023
Viewed by 2404
Abstract
This review summarizes developments in the synthesis and catalytic applications of those heterobimetallic carbene complexes in which at least two different metals are bound to the same ligand by at least one M-C(carbene) bond each. Several new synthetic methods for such complexes yielding [...] Read more.
This review summarizes developments in the synthesis and catalytic applications of those heterobimetallic carbene complexes in which at least two different metals are bound to the same ligand by at least one M-C(carbene) bond each. Several new synthetic methods for such complexes yielding well-defined and thoroughly characterized compounds are presented. The new complexes were found to be catalytically active in several (most often tandem) reactions. In certain cases, the incorporation of two different metals into the same imidazole- or triazol-based NHC-carbene complex resulted in the substantially higher catalytic activity of the heterobimetallic complex compared either to its homobimetallic analogs or to mixtures of comparable mononuclear complex fragments containing the two metals independently. This is a clear demonstration of advantageous metal–metal cooperation within the catalyst. Opposite examples are also discussed, where the heterobimetallic carbene complex proved inferior in relation to its homobimetallic analogs or to mixtures of homonuclear fragments. Full article
(This article belongs to the Special Issue Organometallic Homogeneous Catalysis)
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19 pages, 3904 KiB  
Review
Advances in Nonprecious Metal Homogeneously Catalyzed Formic Acid Dehydrogenation
by Manuel Iglesias and Francisco J. Fernández-Alvarez
Catalysts 2021, 11(11), 1288; https://doi.org/10.3390/catal11111288 - 26 Oct 2021
Cited by 21 | Viewed by 3120
Abstract
Formic acid (FA) possesses a high volumetric concentration of H2 (53 g L−1). Moreover, it can be easily prepared, stored, and transported. Therefore, FA stands out as a potential liquid organic hydrogen carrier (LOHC), which allows storage and transportation of [...] Read more.
Formic acid (FA) possesses a high volumetric concentration of H2 (53 g L−1). Moreover, it can be easily prepared, stored, and transported. Therefore, FA stands out as a potential liquid organic hydrogen carrier (LOHC), which allows storage and transportation of hydrogen in a safe way. The dehydrogenation to produce H2 and CO2 competes with its dehydration to give CO and H2O. For this reason, research on selective catalytic FA dehydrogenation has gained attention in recent years. Several examples of highly active homogenous catalysts based on precious metals effective for the selective dehydrogenation of FA have been reported. Among them are the binuclear iridium-bipyridine catalysts described by Fujita and Himeda et al. (TOF = 228,000 h−1) and the cationic species [IrClCp*(2,2′-bi-2-imidazoline)]Cl (TOF = 487,500 h−1). However, examples of catalytic systems effective for the solventless dehydrogenation of FA, which is of great interest since it allows to reduce the reaction volume and avoids the use of organic solvents that could damage the fuel cell, are scarce. In this context, the development of transition metal catalysts based on cheap and easily available nonprecious metals is a subject of great interest. This work contains a summary on the state of the art of catalytic dehydrogenation of FA in homogeneous phase, together with an account of the catalytic systems based on non-precious metals so far reported. Full article
(This article belongs to the Special Issue Organometallic Homogeneous Catalysis)
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