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Inorganics
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Revealing Reaction Mechanisms in Homogeneous Transition Metal Catalysis
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Revealing Reaction Mechanisms in Homogeneous Transition Metal Catalysis

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Organometallic Chemistry".

Deadline for manuscript submissions: closed (15 October 2017) | Viewed by 56093

Special Issue Editors

Prof. Dr. Axel Klein

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Guest Editor
Department of Chemistry, Institute of Inorganic Chemistry, University of Cologne, D-50939 Cologne, Germany
Interests: transition metal complexes (including organometallic); platinum, palladium, nickel; synthesis; electrochemistry; photophysics; spectroscopy; modelling of catalytic processes
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Bernd Goldfuß

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Guest Editor
Institute for Organic Chemistry, Department of Chemistry, University of Cologne, Cologne, Germany
Interests: ligand-design; metal-catalysis; metal-free catalysis; computational chemistry; organometallic regents
Dr. Jarl Ivar Van der Vlugt

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Guest Editor
Homogeneous, Bioinspired and Supramolecular Catalysis, van ’t Hoff Institute for Molecular Sciences, University of Amsterdam, 1090 GS Amsterdam, The Netherlands
Interests: organometallic chemistry with base and noble metals; redox-active and reactive ligands for homogeneous catalysis; small molecule activation; C‒H functionalization; hydroadditions; dinuclear systems; catalysis in energy research

Special Issue Information

Dear Colleagues,

Man-made homogeneous catalysis with the aid of transition metal compounds looks back on a long history of almost one hundred years. One of the first milestones was probably hydroformylation, worked out by Otto Roelen in the 1930s. However, when considering metalloenzymes in biochemical processes, there has been a lot of homogeneous catalysis using transition metals, long before the technical developments of mankind. For non-transition metal catalysis, the description of the underlying mechanistic steps is usually facilitated by the invariability of the octet rule for the involved light elements. For transition metals, the number of binding partners, spin and oxidation state, in other words, their electronic setting is less clear. Plausibility very often rules the depicted mechanisms instead of consolidated knowledge. However, with largely improved spectroscopic and analytical tools on one hand and dramatically developing quality of quantum chemical calculations on the other, more and more studies seek insight into catalytic mechanisms.

This Special Issue intends to bring together experimental, theoretical, and mixed experimental-theoretical approaches to reveal mechanisms in transition metal catalyzed organic, inorganic, organometallic, and also biochemical transformations. It will focus on the role of the transition metal(s) in binding and activating substrates, transforming them and finally releasing them. This includes the beneficial/cooperating role of non-spectator ligands. Studies dedicated to bringing insight into reaction mechanisms, including tracing or characterization of intermediates or modelling essential reaction steps are welcome.

Prof. Dr. Axel Klein
Prof. Dr. Bernd Goldfuß
Dr. Jarl Ivar van der Vlugt
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Inorganics is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Transition metal catalysis
  • C–C cross-coupling
  • Cyclizations
  • C–H activation
  • C–C activation
  • Small molecule activation
  • Oxygenation
  • Oxidation
  • Hydrogenation
  • Hydroaddition reactions
  • Radical reactions
  • Asymmetric catalysis
  • Mechanistic studies
  • Reactive intermediates
  • In situ spectroscopy
  • Quantum chemical calculations
  • Enzyme modelling
  • Substrate activation
  • Ligand design
  • Cooperative catalysis

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Related Special Issue

Published Papers (9 papers)

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Editorial

Jump to: Research, Review

4 pages, 171 KiB  
Editorial
From Mechanisms in Homogeneous Metal Catalysis to Applications in Chemical Synthesis
by Axel Klein, Bernd Goldfuss and Jarl-Ivar Van der Vlugt
Inorganics 2018, 6(1), 19; https://doi.org/10.3390/inorganics6010019 - 24 Jan 2018
Cited by 3 | Viewed by 3219
Abstract
Man-made homogeneous catalysis with the aid of transition metal compounds looks back on a long history of almost one hundred years. Still, more detailed insight into the underlying mechanisms is warranted. The knowledge of how transition metals with their specific/characteristic properties, such as [...] Read more.
Man-made homogeneous catalysis with the aid of transition metal compounds looks back on a long history of almost one hundred years. Still, more detailed insight into the underlying mechanisms is warranted. The knowledge of how transition metals with their specific/characteristic properties, such as oxidations states, redox chemistry, spin states, kinetics, and coordination preference will contribute to these processes paving the way to optimize existing processes, and to finding new exciting organic, inorganic, and organometallic transformations and to broaden the substrate scope through catalyst design. This special issue collects very recent mechanistic insight from experimental, theoretical, and mixed experimental–theoretical approaches. Full article
(This article belongs to the Special Issue Revealing Reaction Mechanisms in Homogeneous Transition Metal Catalysis)

Research

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2290 KiB  
Article
The Mechanism of Rh-Catalyzed Transformation of Fatty Acids to Linear Alpha olefins
by Sondre H. Hopen Eliasson, Anamitra Chatterjee, Giovanni Occhipinti and Vidar R. Jensen
Inorganics 2017, 5(4), 87; https://doi.org/10.3390/inorganics5040087 - 4 Dec 2017
Cited by 11 | Viewed by 6212
Abstract
Linear alpha olefins (LAOs) are key commodity chemicals and petrochemical intermediates that are currently produced from fossil resources. Fatty acids are the obvious renewable starting material for LAOs, which can be obtained via transition-metal-catalyzed decarbonylative dehydration. However, even the best catalysts that have [...] Read more.
Linear alpha olefins (LAOs) are key commodity chemicals and petrochemical intermediates that are currently produced from fossil resources. Fatty acids are the obvious renewable starting material for LAOs, which can be obtained via transition-metal-catalyzed decarbonylative dehydration. However, even the best catalysts that have been obtained to date, which are based on palladium, are not active and stable enough for industrial use. To provide insight for design of better catalysts, we here present the first computationally derived mechanism for another attractive transition-metal for this reaction, rhodium. By comparing the calculated mechanisms and free energy profiles for the two metals, Pd and Rh, we single out important factors for a facile, low-barrier reaction and for a stable catalyst. While the olefin formation is rate limiting for both of the metals, the rate-determining intermediate for Rh is, in contrast to Pd, the starting complex, (PPh3)2Rh(CO)Cl. This complex largely draws its stability from the strength of the Rh(I)–CO bond. CO is a much less suitable ligand for the high-oxidation state Rh(III). However, for steric reasons, rhodium dissociates a bulkier triphenylphosphine and keeps the carbonyl during the oxidative addition, which is less favorable than for Pd. When compared to Pd, which dissociates two phosphine ligands at the start of the reaction, the catalytic activity of Rh also appears to be hampered by its preference for high coordination numbers. The remaining ancillary ligands leave less space for the metal to mediate the reaction. Full article
(This article belongs to the Special Issue Revealing Reaction Mechanisms in Homogeneous Transition Metal Catalysis)
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3942 KiB  
Article
Reactivity of Zinc Halide Complexes Containing Camphor-Derived Guanidine Ligands with Technical rac-Lactide
by Angela Metz, Joshua Heck, Clara Marie Gohlke, Konstantin Kröckert, Yannik Louven, Paul McKeown, Alexander Hoffmann, Matthew D. Jones and Sonja Herres-Pawlis
Inorganics 2017, 5(4), 85; https://doi.org/10.3390/inorganics5040085 - 30 Nov 2017
Cited by 13 | Viewed by 5685
Abstract
Three new zinc complexes with monoamine–guanidine hybridligands have been prepared, characterized by X-ray crystallography and NMR spectroscopy, and tested in the solvent-free ring-opening polymerization of rac-lactide. Initially the ligands were synthesized from camphoric acid to obtain TMGca and DMEGca and then reacted [...] Read more.
Three new zinc complexes with monoamine–guanidine hybridligands have been prepared, characterized by X-ray crystallography and NMR spectroscopy, and tested in the solvent-free ring-opening polymerization of rac-lactide. Initially the ligands were synthesized from camphoric acid to obtain TMGca and DMEGca and then reacted with zinc(II) halides to form zinc complexes. All complexes have a distorted tetrahedral coordination. They were utilized as catalysts in the solvent-free polymerization of technical rac-lactide at 150 °C. Colorless polylactide (PLA) can be produced and after 2 h conversion up to 60% was reached. Furthermore, one zinc chlorido complex was tested with different qualities of lactide (technical and recrystallized) and with/without the addition of benzyl alcohol as a co-initiator. The kinetics were monitored by in situ FT-IR or 1H NMR spectroscopy. All kinetic measurements show first-order behavior with respect to lactide. The influence of the chiral complexes on the stereocontrol of PLA was examined. Moreover, with MALDI-ToF measurements the end-group of the obtained polymer was determined. DFT and NBO calculations give further insight into the coordination properties. All in all, these systems are robust against impurities and water in the lactide monomer and show great catalytic activity in the ROP of lactide. Full article
(This article belongs to the Special Issue Revealing Reaction Mechanisms in Homogeneous Transition Metal Catalysis)
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2985 KiB  
Article
Ruthenium-Catalyzed Dimerization of 1,1-Diphenylpropargyl Alcohol to a Hydroxybenzocyclobutene and Related Reactions
by Hoang Ngan Nguyen, Naoto Tashima, Takao Ikariya and Shigeki Kuwata
Inorganics 2017, 5(4), 80; https://doi.org/10.3390/inorganics5040080 - 16 Nov 2017
Cited by 3 | Viewed by 4308
Abstract
Propargyl alcohol is a useful synthon in synthetic organic chemistry. We found that the ruthenium(II) complex [Cp*RuCl(diene)] (Cp* = η5-C5Me5; diene = isoprene or 1,5-cyclooctadiene (cod)) catalyzes dimerization of 1,1-diphenylprop-2-yn-1-ol (1,1-diphenylpropargyl alcohol, 1a) at room temperature [...] Read more.
Propargyl alcohol is a useful synthon in synthetic organic chemistry. We found that the ruthenium(II) complex [Cp*RuCl(diene)] (Cp* = η5-C5Me5; diene = isoprene or 1,5-cyclooctadiene (cod)) catalyzes dimerization of 1,1-diphenylprop-2-yn-1-ol (1,1-diphenylpropargyl alcohol, 1a) at room temperature to afford an alkylidenebenzocyclobutenyl alcohol 2a quantitatively. Meanwhile, a stoichiometric reaction of the related hydrido complex [Cp*RuH(cod)] with 1a at 50 °C led to isolation of a ruthenocene derivative 4 bearing a cyclopentadienyl ring generated by dehydrogenative trimerization of 1a. Detailed structures of 2a and 4 were determined by X-ray crystallography. The reaction mechanisms for the formation of 2a and 4 were proposed. Full article
(This article belongs to the Special Issue Revealing Reaction Mechanisms in Homogeneous Transition Metal Catalysis)
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5353 KiB  
Article
Mechanistic Implications for the Ni(I)-Catalyzed Kumada Cross-Coupling Reaction
by Linda Iffland, Anette Petuker, Maurice Van Gastel and Ulf-Peter Apfel
Inorganics 2017, 5(4), 78; https://doi.org/10.3390/inorganics5040078 - 14 Nov 2017
Cited by 24 | Viewed by 6444
Abstract
Herein we report on the cross-coupling reaction of phenylmagnesium bromide with aryl halides using the well-defined tetrahedral Ni(I) complex, [(Triphos)NiICl] (Triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane). In the presence of 0.5 mol % [(Triphos)NiICl], good to excellent yields (75–97%) of the respective [...] Read more.
Herein we report on the cross-coupling reaction of phenylmagnesium bromide with aryl halides using the well-defined tetrahedral Ni(I) complex, [(Triphos)NiICl] (Triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane). In the presence of 0.5 mol % [(Triphos)NiICl], good to excellent yields (75–97%) of the respective coupling products within a reaction time of only 2.5 h at room temperature were achieved. Likewise, the tripodal Ni(II)complexes [(κ2-Triphos)NiIICl2] and [(κ3-Triphos)NiIICl](X) (X = ClO4, BF4) were tested as potential pre-catalysts for the Kumada cross-coupling reaction. While the Ni(II) complexes also afford the coupling products in comparable yields, mechanistic investigations by UV/Vis and electron paramagnetic resonance (EPR) spectroscopy indicate a Ni(I) intermediate as the catalytically active species in the Kumada cross-coupling reaction. Based on experimental findings and density functional theory (DFT) calculations, a plausible Ni(I)-catalyzed reaction mechanism for the Kumada cross-coupling reaction is presented. Full article
(This article belongs to the Special Issue Revealing Reaction Mechanisms in Homogeneous Transition Metal Catalysis)
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4323 KiB  
Article
3-Methylindole-Based Tripodal Tetraphosphine Ruthenium Complexes in N2 Coordination and Reduction and Formic Acid Dehydrogenation
by Fenna F. Van de Watering, Nicol Heijtbrink, Jarl Ivar Van der Vlugt, Wojciech I. Dzik, Bas De Bruin and Joost N. H. Reek
Inorganics 2017, 5(4), 73; https://doi.org/10.3390/inorganics5040073 - 30 Oct 2017
Cited by 5 | Viewed by 4951
Abstract
The ruthenium(II) complexes RuCl2L1H, RuCl2L1CF3, RuCl2L1OMe and RuCl2L2H were synthesized from [Ru(η6-benzene)Cl(μ-Cl)]2 and the corresponding tripodal tris-3-methylindolephosphine-based ligands L1H, L1CF3, L1OMe [...] Read more.
The ruthenium(II) complexes RuCl2L1H, RuCl2L1CF3, RuCl2L1OMe and RuCl2L2H were synthesized from [Ru(η6-benzene)Cl(μ-Cl)]2 and the corresponding tripodal tris-3-methylindolephosphine-based ligands L1H, L1CF3, L1OMe, and L2H. Stoichiometric reduction of these complexes with KC8 yielded the corresponding ruthenium(0) dinitrogen complexes. The latter complexes were studied in the N2 reduction with chlorosilanes and KC8, yielding stoichiometric amounts of the silylamines. The synthesized ruthenium(II) complexes are also active catalysts for the formic acid dehydrogenation reaction. Full article
(This article belongs to the Special Issue Revealing Reaction Mechanisms in Homogeneous Transition Metal Catalysis)
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Review

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14 pages, 2713 KiB  
Review
The Fe Protein: An Unsung Hero of Nitrogenase
by Andrew J. Jasniewski, Nathaniel S. Sickerman, Yilin Hu and Markus W. Ribbe
Inorganics 2018, 6(1), 25; https://doi.org/10.3390/inorganics6010025 - 3 Feb 2018
Cited by 30 | Viewed by 8267
Abstract
Although the nitrogen-fixing enzyme nitrogenase critically requires both a reductase component (Fe protein) and a catalytic component, considerably more work has focused on the latter species. Properties of the catalytic component, which contains two highly complex metallocofactors and catalyzes the reduction of N [...] Read more.
Although the nitrogen-fixing enzyme nitrogenase critically requires both a reductase component (Fe protein) and a catalytic component, considerably more work has focused on the latter species. Properties of the catalytic component, which contains two highly complex metallocofactors and catalyzes the reduction of N2 into ammonia, understandably making it the “star” of nitrogenase. However, as its obligate redox partner, the Fe protein is a workhorse with multiple supporting roles in both cofactor maturation and catalysis. In particular, the nitrogenase Fe protein utilizes nucleotide binding and hydrolysis in concert with electron transfer to accomplish several tasks of critical importance. Aside from the ATP-coupled transfer of electrons to the catalytic component during substrate reduction, the Fe protein also functions in a maturase and insertase capacity to facilitate the biosynthesis of the two-catalytic component metallocofactors: fusion of the [Fe8S7] P-cluster and insertion of Mo and homocitrate to form the matured [(homocitrate)MoFe7S9C] M-cluster. These and key structural-functional relationships of the indispensable Fe protein and its complex with the catalytic component will be covered in this review. Full article
(This article belongs to the Special Issue Revealing Reaction Mechanisms in Homogeneous Transition Metal Catalysis)
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18 pages, 3644 KiB  
Review
Exploring Mechanisms in Ni Terpyridine Catalyzed C–C Cross-Coupling Reactions—A Review
by Yulia H. Budnikova, David A. Vicic and Axel Klein
Inorganics 2018, 6(1), 18; https://doi.org/10.3390/inorganics6010018 - 23 Jan 2018
Cited by 52 | Viewed by 9435
Abstract
In recent years, nickel has entered the stage for catalyzed C–C cross-coupling reactions, replacing expensive palladium, and in some cases enabling the use of new substrate classes. Polypyridine ligands have played an important role in this development, and the prototypical tridentate 2,2′:6′,2′′-terpyridine (tpy) [...] Read more.
In recent years, nickel has entered the stage for catalyzed C–C cross-coupling reactions, replacing expensive palladium, and in some cases enabling the use of new substrate classes. Polypyridine ligands have played an important role in this development, and the prototypical tridentate 2,2′:6′,2′′-terpyridine (tpy) stands as an excellent example of these ligands. This review summarizes research that has been devoted to exploring the mechanistic details in catalyzed C–C cross-coupling reactions using tpy-based nickel systems. Full article
(This article belongs to the Special Issue Revealing Reaction Mechanisms in Homogeneous Transition Metal Catalysis)
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2132 KiB  
Review
Redox-Induced Aromatic C–H Bond Functionalization in Metal Complex Catalysis from the Electrochemical Point of View
by Yulia H. Budnikova, Yulia B. Dudkina and Mikhail N. Khrizanforov
Inorganics 2017, 5(4), 70; https://doi.org/10.3390/inorganics5040070 - 16 Oct 2017
Cited by 32 | Viewed by 6108
Abstract
This review generalizes and specifies the oxidizing ability of a number of oxidants used in palladium (Pd)-catalyzed aromatic C–H functionalizations. The redox potentials have been analyzed as the measure of oxidant strength and applied to the reasoning of the efficiency of known reactions [...] Read more.
This review generalizes and specifies the oxidizing ability of a number of oxidants used in palladium (Pd)-catalyzed aromatic C–H functionalizations. The redox potentials have been analyzed as the measure of oxidant strength and applied to the reasoning of the efficiency of known reactions where catalytic cycles include cyclometalated palladium complexes (and other organopalladium key intermediates). Full article
(This article belongs to the Special Issue Revealing Reaction Mechanisms in Homogeneous Transition Metal Catalysis)
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