3-Methylindole-Based Tripodal Tetraphosphine Ruthenium Complexes in N2 Coordination and Reduction and Formic Acid Dehydrogenation

Watering, Fenna F. van de; Heijtbrink, N.; Vlugt, Jarl Ivar van der; Dzik, Wojciech I.; Bruin, Bas de; Reek, Joost N. H.

doi:10.3390/inorganics5040073

Cited by 5 publications

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“…The work by van de Watering, Heijtebrink, van der Vlugt, Dzik, de Bruin and Reek describes the coordination chemistry of a series of tripodal tetraphosphane ligands (tris-(3-methylindolephosphane)phosphanes = PP 3 ) with ruthenium(II) [27]. The reduction of these species under an N 2 atmosphere led to isolable Ru-N 2 complexes.…”

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From Mechanisms in Homogeneous Metal Catalysis to Applications in Chemical Synthesis

2018

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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.At the very end of the 19th century, Alfred Werner established the basis of our modern understanding of (transition) metal complexes [1]. When Otto Roelen discovered and developed the hydroformylation reaction (or Oxo Process) in the late 1930s, probably the first milestone in homogeneous catalysis, serendipity played an important role [2,3]. A deeper understanding of the specific interactions of ligands and metals came only later with the development of binding concepts such as the ligand field theory and the molecular orbital theory, e.g., the Dewar-Chatt-Duncanson model, which was developed in the 1950s for the binding of olefins to transition metals [4]. Originally dedicated to the binding situation of the complex anion of the Zeise salt [PtCl 3 (ethene)] -, it soon became clear that homogeneously metal-catalyzed transformations of olefins can be described and understood using this concept [4][5][6][7]. Probably the most prominent examples of such olefin complexes are the Pd derivatives of the Zeise anion [PdCl 3 (olefin)] − , which were the pivotal species of today's technically most important organocatalytic process, the Wacker Process (or Wacker Oxidation), which was developed starting in the 1950s [7][8][9][10].About 80 years after Roelen's hydroformylation, on a list of recently identified "holy grails" in chemistry "perfect catalysis" is prominently in the top ten [11] and homogeneous transition metal catalysis provides the basis for many desired transformations, e.g., in C-H aminations, in site-selective bond activations, for the functionalization of alkanes or in oxidative couplings yielding complex target molecules. Even since the rise of "metal-free" organo-catalysis at the beginning of our millennium and its enormous impact on organic transformations, the meanwhile established "classical" (transition) metal mediated applications reside as solid pillars in the toolbox for chemical synthesis [12][13][14]. Recent Nobel Prizes in chemistry, i.e., 2010 to Richard F. Heck, Ei-ichi Negishi and Akira Suzuki, 2005 to Yves Chauvin, Robert H. Grubbs and Richard R. Schrock, as well as 2001 to William S. Knowles, Ryoji Noyori and K. Barry Sharpless [14,15] clearly highlight homogeneous transition metal catalysis as an outstanding discipline, crucial for various are...

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From Mechanisms in Homogeneous Metal Catalysis to Applications in Chemical Synthesis

2018

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Well‐defined Nickel P₃C Complexes as Hydrogenation Catalysts of N‐Heteroarenes Under Mild Conditions

et al. 2022

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The reactivity of metal complexes can be primarily controlled by their coordinating ligands. Electronic effects and geometric restrictions imposed by ligands, prototypically modify their reactivity, but are not always straightforward accessible. In the course of the study, we explored new C3‐symmetric organometallic nickel (II) complexes ((P3C)Ni)) with the particularity of having a metalated apical carbon trans to a labile coordination site readily available as a catalytic site. The synthetic methodology allowed to tune the electronic properties by introducing substituents on the phosphines. We studied the nature of the C−Ni bond by X‐ray absorption spectroscopy (XAS) and DFT and applied them to the catalytic hydrogenation of quinolines with a good chemical scope and group tolerance. 1H‐NMR monitoring, isotopic labelling, and computational studies are consistent with a heterolytic activation of the dihydrogen molecule after forming a σ‐H2 adduct trans to the metalated carbon.

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Coordination of 3‐Methylindole‐Based Tripodal Tetraphosphine Ligands to Iron(+II), Cobalt(+II), and Nickel(+II) and Investigations of their Subsequent Two‐Electron Reduction

et al. 2018

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We report the coordination chemistry of indole based tripodal tetraphosphine ligands to iron(II), cobalt(II) and nickel(II). These complexes are formed by simple synthetic protocols and were characterized by a combination of spectroscopic techniques and single‐crystal X‐ray analysis. The molecular structures as determined by X‐ray diffraction show that the geometry of the nickel and cobalt complexes are distorted trigonal bipyramidal. The monocationic iron(II) complexes also have distorted trigonal bipyramidal geometries, but the dicationic analogue has an octahedral geometry. Two‐electron reduction of the cobalt(+II) and the nickel(+II) complexes in the presence of N2 did not lead to the coordination of N2. In contrast, two‐electron reduction of the iron(+II) complexes did lead to coordination of dinitrogen to the iron center. The Fe0N2 L1H complex has a trigonal bipyramidal geometry, and the N–N bond length of the coordinated dinitrogen ligand is longer than that of free dinitrogen, indicating that coordination to this iron(0) complex results in activation of the N≡N bond.

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3-Methylindole-Based Tripodal Tetraphosphine Ruthenium Complexes in N2 Coordination and Reduction and Formic Acid Dehydrogenation

Cited by 5 publications

References 40 publications

From Mechanisms in Homogeneous Metal Catalysis to Applications in Chemical Synthesis

From Mechanisms in Homogeneous Metal Catalysis to Applications in Chemical Synthesis

Well‐defined Nickel P₃C Complexes as Hydrogenation Catalysts of N‐Heteroarenes Under Mild Conditions

Coordination of 3‐Methylindole‐Based Tripodal Tetraphosphine Ligands to Iron(+II), Cobalt(+II), and Nickel(+II) and Investigations of their Subsequent Two‐Electron Reduction

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3-Methylindole-Based Tripodal Tetraphosphine Ruthenium Complexes in N2 Coordination and Reduction and Formic Acid Dehydrogenation

Cited by 5 publications

References 40 publications

From Mechanisms in Homogeneous Metal Catalysis to Applications in Chemical Synthesis

From Mechanisms in Homogeneous Metal Catalysis to Applications in Chemical Synthesis

Well‐defined Nickel P3C Complexes as Hydrogenation Catalysts of N‐Heteroarenes Under Mild Conditions

Coordination of 3‐Methylindole‐Based Tripodal Tetraphosphine Ligands to Iron(+II), Cobalt(+II), and Nickel(+II) and Investigations of their Subsequent Two‐Electron Reduction

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Well‐defined Nickel P₃C Complexes as Hydrogenation Catalysts of N‐Heteroarenes Under Mild Conditions