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Water-catalyzed iron-molybdenum carbyne formation in bimetallic acetylene transformation.

ABSTRACT: Transition metal carbyne complexes are of fundamental importance in carbon-carbon bond formation, alkyne metathesis, and alkyne coupling reactions. Most reported iron carbyne complexes are stabilized by incorporating heteroatoms. Here we show the synthesis of bioinspired FeMo heterobimetallic carbyne complexes by the conversion of C₂H₂ through a diverse series of intermediates. Key reactions discovered include the reduction of a μ-η²:η²-C₂H₂ ligand with a hydride to produce a vinyl ligand (μ-η¹:η²-CH = CH₂), tautomerization of the vinyl ligand to a carbyne (μ-CCH₃), and protonation of either the vinyl or the carbyne compound to form a hydrido carbyne heterobimetallic complex. Mechanistic studies unveil the pivotal role of H₂O as a proton shuttle, facilitating the proton transfer that converts the vinyl group to a bridging carbyne.

SUBMITTER: Zhai X

PROVIDER: S-EPMC11375111 | biostudies-literature | 2024 Sep

REPOSITORIES: biostudies-literature

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Water-catalyzed iron-molybdenum carbyne formation in bimetallic acetylene transformation.

Zhai Xiaofang X Xue Minghui M Zhao Qiuting Q Zheng Qiucui Q Song Datong D Tung Chen-Ho CH Wang Wenguang W

Nature communications 20240904 1

Transition metal carbyne complexes are of fundamental importance in carbon-carbon bond formation, alkyne metathesis, and alkyne coupling reactions. Most reported iron carbyne complexes are stabilized by incorporating heteroatoms. Here we show the synthesis of bioinspired FeMo heterobimetallic carbyne complexes by the conversion of C2H2 through a diverse series of intermediates. Key reactions discovered include the reduction of a μ-η2:η2-C2H< ...[more]

PMID: 39232032

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Project description:Bimetallic heterogeneous catalysts combining group 9 metals (Rh, Ir) or group 10 metals (Ni, Pd, Pt) with Mo on a silica-based support have been synthesized via surface organometallic chemistry and assessed in their catalytic activity for the hydrodeoxygenation (HDO) of alcohols with particular emphasis on the structural evolution of the catalysts and the role of Mo. The investigation was conducted with an air-free approach to isolate any sample alterations exclusively to those caused by the reaction. Structural analysis was performed using a combination of (S)TEM, IR, and XAS. It was found that Ir-Mo/SiO2, Rh-Mo/SiO2, and Pt-Mo/SiO2 display high activity for primary, secondary, and tertiary alcohol deoxygenation, while Pd-Mo/SiO2 selectively catalyses tertiary alcohol deoxygenation. Other combinations as well as the corresponding monometallic materials do not display the same activity. X-ray absorption spectroscopy confirmed metallic states for M (M = Ni, Rh, Pd, Ir, or Pt), while Mo K-edge XANES showed varying amounts of Mo(0), Mo(iv) and Mo(vi) depending on the metal counterpart in fresh materials, and indicated complete conversion of Mo(vi) to lower oxidation states (IV and 0) during the reaction. For Rh, Pd, Ir, and Pt, alloy formation (M-Mo) was identified via M-Mo paths in EXAFS and supported by CO-IR spectroscopy. In contrast to Ir, Rh, and Pt, where some Mo(0) is present at the nanoparticle surface, Pd-Mo forms an alloy but likely retains Mo in the nanoparticle core, as suggested by CO-IR spectroscopy and CO-chemisorption. Reactivity studies suggest that tertiary alcohols primarily undergo dehydration-hydrogenation, evidenced by olefin formation with MoO x /SiO2, as well as Ir/SiO2 and Ir-Mo/SiO2 under inert conditions. In contrast, primary and secondary alcohols follow a different mechanism, correlated with the presence of metallic Mo species on the nanoparticle surface, highlighting their role in C-O bond activation. These findings provide new insights into the structure-activity relationships of Mo-based bimetallic catalysts, underscoring the influence of Mo in different oxidation states and strong substrate dependence on mechanistic pathways.

Dataset Information

Water-catalyzed iron-molybdenum carbyne formation in bimetallic acetylene transformation.

Publications

Water-catalyzed iron-molybdenum carbyne formation in bimetallic acetylene transformation.

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