Electron-deficient linear tetranuclear ruthenium(I) carboxylate chains

Hemilabile ligands have been applied extensively in transition metal catalysis, but preparations of these molecules typically require multistep synthesis.Here, modular assembly of diverse phosphine-amide ligands, including related axially chiral compounds, is first reported through ruthenium-catalyzed CÀ H activation of phosphines with isocyanate directed by phosphorus(III) atoms. High reactivity and regioselectivity can be obtained by using a Ru 3 (CO) 12 catalyst with a mono-N-protected amino acid ligand. This transformation significantly expands the pool of phosphine-amide ligands, some of which have shown excellent efficiency for asymmetric catalysis. More broadly, the discovery constitutes a proof of principle for facile construction of hemilabile ligands directly from the parent monodentate phosphines by CÀ H activation with ideal atom, step and redox economy. Several dinuclear ruthenium complexes were characterized by single-crystal X-ray diffraction analysis revealing the key mechanistic features of this transformation.

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Ru₃(CO)₁₂‐Catalyzed Modular Assembly of Hemilabile Ligands by C−H Activation of Phosphines with Isocyanates

Lin

Zhang

et al. 2022

Angewandte Chemie

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Ru₃(CO)₁₂‐Catalyzed Modular Assembly of Hemilabile Ligands by C−H Activation of Phosphines with Isocyanates

Lin

Zhang

et al. 2022

Angew Chem Int Ed

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Encapsulating ruthenium in silica using a single source precursor: Differing outcomes for a cycloaddition reaction

Barik

Ganguly

Garcı́a

et al. 2020

Inorganica Chimica Acta

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Electron-deficient linear tetranuclear ruthenium(I) carboxylate chains

Cited by 6 publications

References 17 publications

Ru₃(CO)₁₂‐Catalyzed Modular Assembly of Hemilabile Ligands by C−H Activation of Phosphines with Isocyanates

Ru₃(CO)₁₂‐Catalyzed Modular Assembly of Hemilabile Ligands by C−H Activation of Phosphines with Isocyanates

Ru₃(CO)₁₂‐Catalyzed Modular Assembly of Hemilabile Ligands by C−H Activation of Phosphines with Isocyanates

Encapsulating ruthenium in silica using a single source precursor: Differing outcomes for a cycloaddition reaction

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Electron-deficient linear tetranuclear ruthenium(I) carboxylate chains

Cited by 6 publications

References 17 publications

Ru3(CO)12‐Catalyzed Modular Assembly of Hemilabile Ligands by C−H Activation of Phosphines with Isocyanates

Ru3(CO)12‐Catalyzed Modular Assembly of Hemilabile Ligands by C−H Activation of Phosphines with Isocyanates

Ru3(CO)12‐Catalyzed Modular Assembly of Hemilabile Ligands by C−H Activation of Phosphines with Isocyanates

Encapsulating ruthenium in silica using a single source precursor: Differing outcomes for a cycloaddition reaction

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Product

Resources

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Ru₃(CO)₁₂‐Catalyzed Modular Assembly of Hemilabile Ligands by C−H Activation of Phosphines with Isocyanates

Ru₃(CO)₁₂‐Catalyzed Modular Assembly of Hemilabile Ligands by C−H Activation of Phosphines with Isocyanates

Ru₃(CO)₁₂‐Catalyzed Modular Assembly of Hemilabile Ligands by C−H Activation of Phosphines with Isocyanates