Mechanistic Insight into Synergistic Catalysis of Olefin Hydrogenation by a Hetero-Dinuclear Ru<sup>II</sup>–Co<sup>II</sup> Complex with Adjacent Reaction Sites

Hong, Dachao; Ohgomori, Yuji; Shimoyama, Yoshihiro; Kotani, Hiroaki; Ishizuka, Tomoya; Kon, Yoshihiro; Kojima, Takahiko

doi:10.1021/acs.inorgchem.9b02104

Cited by 5 publications

(10 citation statements)

References 26 publications

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“…It is reasonable to propose that the MeOH molecule bound to a labile Ni II center should be easily substituted by a H 2 O molecule when 2 is dissolved in an aqueous buffer solution. Because a Co II center of a heterodinuclear Ru II −Co II complex in our previous report 36 can activate methanol as a proton source to enhance hydrogenation reactions, a similar phenomenon may occur in the H 2 evolution by the dinuclear Ir III −M II complexes. Thus, the Co II center in 1 and the Co II center in 2 are also expected to contribute to the activation of the aqua ligand to enhance H 2 evolution.…”

Section: ■ Results and Discussionmentioning

confidence: 64%

“…Synthesis and Characterization of Heterodinuclear Metal Complexes. Heterodinuclear complexes 1−3 were obtained by reacting [Ir III (Cp*)(Hbpp)(Cl)]BF 4 38 and the respective [M II (dipc)(H 2 O) n ] (M = Co for 1, Ni for 2, and Cu for 3) 36,39 in MeOH. The formation of complexes 1−3 was confirmed by ESI-TOF-MS measurements (Figure S1).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…ESI-TOF-MS spectra were measured on a JEOL JMS-T100CS spectrometer. The Mebpp ligand, [Co II (dipc)(H 2 O) 3 ], [Ni II (dipc)(H 2 O) 3 ], [Cu II (dipc)(H 2 O) 2 ], and [Ir III (Cp*)(Cl)(Hbpp)]BF 4 were synthesized according to the reported procedure.…”

Section: Methodsmentioning

confidence: 99%

“…36 In the hydrogenation reactions by the Ru−Co heterodinuclear complex, the Ru center is converted to be a Ru−hydrido complex and the Co center acts as an activator of a proton source. 36 Thus, we assumed that the same strategy would be effective for the H 2 evolution from formic acid dehydrogenation. On the basis of the synthesis strategy of the heterodinuclear Ru−Co complex, we herein design and synthesize a series of novel heterodinuclear Ir III (2), or Cu (3); Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl] as shown in Chart 1, as catalysts for H 2 evolution based on formic acid dehydrogenation in water.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Previously, we reported a heterodinuclear Ru–Co complex, [Ru II ( p -cymene)(μ-bpp)(Cl)Co II (dipc)(H 2 O)] [ p -cymene = 4-isopropyltoluene, H 2 dipc = 2,6-pyridinedicarboxylic acid, and Hbpp = 3,5-bis(2-pyridyl)-pyrazole], in which Hbpp was used as a dinucleating and structure-directing ligand, to conduct catalytic hydrogenation of alkenes with use of NaBH 4 as a hydride source . In the hydrogenation reactions by the Ru–Co heterodinuclear complex, the Ru center is converted to be a Ru–hydrido complex and the Co center acts as an activator of a proton source . Thus, we assumed that the same strategy would be effective for the H 2 evolution from formic acid dehydrogenation.…”

Section: Introductionmentioning

confidence: 99%

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Cooperative Effects of Heterodinuclear Ir^III–M^II Complexes on Catalytic H₂ Evolution from Formic Acid Dehydrogenation in Water

et al. 2020

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Novel heterodinuclear IrIII–MII complexes (M = Co, Ni, or Cu) with two adjacent reaction sites were synthesized by using 3,5-bis(2-pyridyl)-pyrazole (Hbpp) as a structure-directing ligand and employed as catalysts for H2 evolution through formic acid dehydrogenation in water. A cooperative effect of the hetero-metal centers was observed in the H2 evolution in comparison with the corresponding mononuclear IrIII and MII complexes as the components of the IrIII–MII complexes. The H2 evolution rate for the IrIII–MII complexes was at most 350-fold higher than that of the mononuclear IrIII complex. The catalytic activity increased in the following order: IrIII–CuII complex < IrIII–CoII complex < IrIII–NiII complex . The IrIII–H intermediates of the IrIII–MII complexes were successfully detected by ultraviolet–visible, 1H nuclear magnetic resonance, and ESI-TOF-MS spectra. The catalytic enhancement of H2 evolution by the IrIII–MII complexes indicates that the IrIII–H species formed in the IrIII moiety act as reactive species and the MII moieties act as acceleration sites by the electronic effect from the MII center to the IrIII center through the bridging bpp– ligand. The IrIII–MII complexes may also activate H2O at the 3d MII centers as a proton source to facilitate H2 evolution. In addition, the affinity of formate for the IrIII–MII complexes was investigated on the basis of Michaelis–Menten plots; the IrIII–CoII and IrIII–NiII complexes exhibited affinities that were relatively higher than that of the IrIII–CuII complex. The catalytic mechanism of H2 evolution by the IrIII–MII complexes was revealed on the basis of spectroscopic detection of reaction intermediates, kinetic analysis, and isotope labeling experiments.

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Section: ■ Results and Discussionmentioning

confidence: 64%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Cooperative Effects of Heterodinuclear Ir^III–M^II Complexes on Catalytic H₂ Evolution from Formic Acid Dehydrogenation in Water

et al. 2020

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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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Bimetallic Rhodium Complexes: Precatalyst Activation-Triggered Bimetallic Enhancement for the Hydrosilylation Transformation

et al. 2023

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To explore how to access bimetallic catalysts that can outperform their monometallic analogues, a set of mono- and bimetallic NHC/phosphine (NHC = N-heterocyclic carbene)-ligated rhodium(I) complexes were designed, synthesized, and characterized. The complexes were used as catalysts for the intermolecular hydrosilylation of diphenylacetylene. All four catalysts displayed significantly faster catalytic rates than the related complexes reported previously containing NHC/pyrazolyl donor ligands. The bimetallic catalyst design led to enhanced catalytic activity over the monometallic analogue. The data revealed that the degree of bimetallic enhancement was highly dependent on the reaction conditions, coligands used, and the substrate addition order. The catalytic trends, in combination with mechanistic studies using individual substrates and density functional theory calculations, exposed that the bimetallic benefits were strongly linked to the catalyst activation procedure.

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Mechanistic Insight into Synergistic Catalysis of Olefin Hydrogenation by a Hetero-Dinuclear Ru^II–Co^II Complex with Adjacent Reaction Sites

Cited by 5 publications

References 26 publications

Cooperative Effects of Heterodinuclear Ir^III–M^II Complexes on Catalytic H₂ Evolution from Formic Acid Dehydrogenation in Water

Cooperative Effects of Heterodinuclear Ir^III–M^II Complexes on Catalytic H₂ Evolution from Formic Acid Dehydrogenation in Water

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

Bimetallic Rhodium Complexes: Precatalyst Activation-Triggered Bimetallic Enhancement for the Hydrosilylation Transformation

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Mechanistic Insight into Synergistic Catalysis of Olefin Hydrogenation by a Hetero-Dinuclear RuII–CoII Complex with Adjacent Reaction Sites

Cited by 5 publications

References 26 publications

Cooperative Effects of Heterodinuclear IrIII–MII Complexes on Catalytic H2 Evolution from Formic Acid Dehydrogenation in Water

Cooperative Effects of Heterodinuclear IrIII–MII Complexes on Catalytic H2 Evolution from Formic Acid Dehydrogenation in Water

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

Bimetallic Rhodium Complexes: Precatalyst Activation-Triggered Bimetallic Enhancement for the Hydrosilylation Transformation

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Product

Resources

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Mechanistic Insight into Synergistic Catalysis of Olefin Hydrogenation by a Hetero-Dinuclear Ru^II–Co^II Complex with Adjacent Reaction Sites

Cooperative Effects of Heterodinuclear Ir^III–M^II Complexes on Catalytic H₂ Evolution from Formic Acid Dehydrogenation in Water

Cooperative Effects of Heterodinuclear Ir^III–M^II Complexes on Catalytic H₂ Evolution from Formic Acid Dehydrogenation in Water