Formate-driven catalysis and mechanism of an iridium–copper complex for selective aerobic oxidation of aromatic olefins in water

Shimoyama, Yoshihiro; Kitagawa, Yasutaka; Ohgomori, Yuji; Kon, Yoshihiro; Hong, Dachao

doi:10.1039/d0sc06634f

Cited by 7 publications

(3 citation statements)

References 61 publications

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“…[3,4,18,5,6,[12][13][14][15][16][17] Thus the spatial and electronic relationship between the two metals is extremely important for MMC, and is dictated by the scaffolding ligands. Significant success has been attained with ligands such as expanded pincers, [15,[19][20][21][22][23][24] fused mononucleating multidentate systems, [25][26][27][28][29] and macrocycles, [17,[30][31][32] which can be either flexible or rigid (Figure 1). Rigid macrocyclic ligands typically offer trans reactive sites on either face of the macrocycle, such as in quintessential monometallic porphyrins and phthalocyanines.…”

Section: Introductionmentioning

confidence: 99%

Bimetallic Nickel Complexes Supported by a Planar Macrocyclic Diphosphoranide Ligand

Delaney

Doan

et al. 2023

Chemistry A European J

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Metal-metal cooperativity is emerging as an important strategy in catalysis. This requires appropriate ligand scaffolds that can support two metals in close proximity. Here we report nickel-promoted formation of a dinucleating planar macrocyclic ligand that can support bimetallic dinickel(II) and dinickel(I) complexes. Reaction outcomes can be tuned by variation of the substituents and reaction conditions to favour dinucleating macrocyclic, mononucleating macrocyclic or conventional pincer architectures.

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Section: Introductionmentioning

confidence: 99%

Bimetallic Nickel Complexes Supported by a Planar Macrocyclic Diphosphoranide Ligand

Delaney

Doan

et al. 2023

Chemistry A European J

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“…Similar [Cu II ;Ir III ] complexes exhibited high catalytic activity for the aerobic oxidation of olefins, especially compared with their monometallic counterparts, but no indication of a synergistic mechanism was found. The increase in reactivity is probably due to a tuning of the stereoelectronic environment of the Ir III center [ 144 ].…”

Section: Heterobimetallic Complexes In Homogeneous Catalysismentioning

confidence: 99%

Added Complexity!—Mechanistic Aspects of Heterobimetallic Complexes for Application in Homogeneous Catalysis

Fickenscher

Hey‐Hawkins

2023

Molecules

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Inspired by multimetallic assemblies and their role in enzyme catalysis, chemists have developed a plethora of heterobimetallic complexes for application in homogeneous catalysis. Starting with small heterobimetallic complexes with σ-donating and π-accepting ligands, such as N-heterocyclic carbene and carbonyl ligands, more and more complex systems have been developed over the past two decades. These systems can show a significant increase in catalytic activity compared with their monometallic counterparts. This increase can be attributed to new reaction pathways enabled by the presence of a second metal center in the active catalyst. This review focuses on mechanistic aspects of heterobimetallic complexes in homogeneous catalysis. Depending on the type of interaction of the second metal with the substrates, heterobimetallic complexes can be subdivided into four classes. Each of these classes is illustrated with multiple examples, showcasing the versatility of both, the types of interactions possible, and the reactions accessible.

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“…Utilizing synergistic effects in heterobimetallic complexes has only recently been employed. However, in all systems currently available, an additional electronic interaction is highly likely. − …”

Section: Introductionmentioning

confidence: 99%

Stronger Together! Mechanistic Investigation into Synergistic Effects during Homogeneous Carbon Dioxide Hydrogenation Using a Heterobimetallic Catalyst

Fickenscher

Lönnecke

Müller³

et al. 2023

Inorg. Chem.

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A series of group 6 heterobimetallic complexes [M0;IrIII] (M = Cr, Mo, W) were synthesized and fully characterized, and the catalytic behavior was studied. The heterobimetallic complex [Mo0;IrIII] (C1) was by far the most active and has shown a considerable synergistic effect, with both metals actively participating in homogeneous carbon dioxide hydrogenation, leading to formate salts. Based on theoretical calculations, the synergistic interaction is due to Pauli repulsion, lowering the transition state and thus enabling higher catalytic activity. The mechanism of both the hydrogenation itself and the synergistic interaction was studied by NMR spectroscopy, kinetic measurements, and theoretical calculations. The homogeneous nature of the reaction was proven using in situ high-pressure (HP) NMR experiments. The same experiments also showed that the octahedral Mo(CO)3P3 moiety of the complex is stable under the reaction conditions. The hydride complex is the resting state because the hydride transfer is the rate-determining step. This is supported by kinetic measurements, in situ HP NMR experiments, and theoretical calculations and is in contrast to the monometallic IrIII counterpart of C1.

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Formate-driven catalysis and mechanism of an iridium–copper complex for selective aerobic oxidation of aromatic olefins in water

Abstract: A hetero-dinuclear IrIII-CuII complex with two adjacent sites was employed as a catalyst for the aerobic oxidation of aromatic olefins driven by formate in water. An IrIII-H intermediate, generated from...

Cited by 7 publications

References 61 publications

Bimetallic Nickel Complexes Supported by a Planar Macrocyclic Diphosphoranide Ligand

Bimetallic Nickel Complexes Supported by a Planar Macrocyclic Diphosphoranide Ligand

Added Complexity!—Mechanistic Aspects of Heterobimetallic Complexes for Application in Homogeneous Catalysis

Stronger Together! Mechanistic Investigation into Synergistic Effects during Homogeneous Carbon Dioxide Hydrogenation Using a Heterobimetallic Catalyst

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