Reactivity and Catalysis at Sites Trans to the [Ru–Ru] Bond

Dutta, Indranil; Sengupta, Gautam; Bera, Jitendra K.

doi:10.1007/3418_2015_162

Cited by 3 publications

(1 citation statement)

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“…The prospect of cooperative participation of metal ions renders the bimetallic complexes as potential catalysts for organic transformations . Metal–metal bonded complexes are particularly interesting because of enforced proximity between the metals and the ability of the dimetal core to attain valence delocalization . Elementary oxidative addition and reductive elimination processes are more favored on a bimetallic platform than on a single-metal entity .…”

Section: Introductionmentioning

confidence: 99%

Acceptorless Dehydrogenation of Alcohols on a Diruthenium(II,II) Platform

et al. 2016

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The diruthenium(II,II) complex [Ru 2 (L 1 )(OAc) 3 ]Cl (1), spanned by a naphthyridine-diimine ligand and bridged by three acetates, has been synthesized. The catalytic efficacy of complex 1 has been evaluated for the acceptorless dehydrogenation (AD) of alcohols and for the dehydrogenative coupling reactions of alcohols with Wittig reagents. The diruthenium(II,II) complex is an excellent catalyst for AD of a diverse range of alcohols, and it is shown to be particularly effective for the conversion of primary alcohols to the corresponding aldehydes without undesired side products such as esters. Triphenylphosphonium ylides in a one-pot reaction with alcohols afforded the corresponding olefins in high yields with excellent E selectivity. The liberated dihydrogen gas was identified and measured to be 1 equiv with respect to alcohol. Deuteration studies with PhCD 2 OH revealed the absence of isotope scrambling in the product, indicating the involvement of a Ru-monohydride intermediate. Kinetic studies and DFT calculations suggest a low-energy bimetallic β-hydride elimination pathway where rate-limiting intramolecular proton transfer from alcohol to metal-bound hydride constitutes the dehydrogenation step. The general utility of metal−metal bonded compounds for alcohol AD and subsequent coupling reactions is demonstrated here.

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Section: Introductionmentioning

confidence: 99%

Acceptorless Dehydrogenation of Alcohols on a Diruthenium(II,II) Platform

et al. 2016

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Acceptorless Alcohol Dehydrogenation: A Mechanistic Perspective

Pandey

Dutta

Bera

2016

Proc. Natl. Acad. Sci., India, Sect. A Phys. Sci.

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Metal–Metal Bonds in Catalysis

2016

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Transition metals can assemble to form multinuclear complexes by engaging in direct metal-to-metal interactions. Metal–metal covalent bonds provide a large perturbation in electronic structure, relative to mononuclear metal ions, and the unique properties of these dinuclear fragments can be harnessed in a broad range of applicationsfor example, as chromophores in photochemical processes, redox centers in molecular electronics, or structural elements in metal–organic materials. There is a growing body of evidence that metal–metal bonds may also be formed under conditions relevant to catalysis and play a key role in transformations that were previously assumed to only involve mononuclear species. These findings have stimulated interest in characterizing multinuclear reaction pathways and developing well-defined multinuclear platforms as catalytic active sites. In this Perspective, we present case studies in this emerging area of catalysis research, emphasizing the impact of metal–metal bonding in either enhancing or depressing the rate and/or selectivity of a catalytic organic transformation.

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Reactivity and Catalysis at Sites Trans to the [Ru–Ru] Bond

Cited by 3 publications

References 250 publications

Acceptorless Dehydrogenation of Alcohols on a Diruthenium(II,II) Platform

Acceptorless Dehydrogenation of Alcohols on a Diruthenium(II,II) Platform

Acceptorless Alcohol Dehydrogenation: A Mechanistic Perspective

Metal–Metal Bonds in Catalysis

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