Exceedingly Facile PhX Activation (X=Cl, Br, I) with Ruthenium(II): Arresting Kinetics, Autocatalysis, and Mechanisms

Miloserdov, Fedor M.; McKay, David; Muñoz, Bianca K.; Samouei, Hamidreza; Macgregor, Stuart A.; Grushin, Vladimir V.

doi:10.1002/ange.201501996

Cited by 5 publications

(1 citation statement)

References 25 publications

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“…Bulk solvent effects were modelled using Truhlar's SMD continuum solvent model 42 and empirical dispersion corrections were added with the D3 version of Grimme's dispersion. [43][44][45] Both corrections were made on the gas phase geometries by single point calculations. All energies reported throughout the text are Zero Point corrected Potential Energies in dichloromethane.…”

Section: Computational Detailsmentioning

confidence: 99%

Activation of Small Molecules by the Metal–Amido Bond of Rhodium(III) and Iridium(III) (η⁵-C₅Me₅)M-Aminopyridinate Complexes

et al. 2017

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We report the synthesis and structural characterization of five-coordinate complexes of rhodium and iridium of the type [(η-CMe)M(N^N)] (3-M), where N^N represents the aminopyridinate ligand derived from 2-NH(Ph)-6-(Xyl)CHN (Xyl = 2,6-MeCH). The two complexes were isolated as salts of the BAr anion (BAr = B[3,5-(CF)CH]). The M-N bond of complexes 3-M readily activated CO, CH, and H. Thus, compounds 3-M reacted with CO under ambient conditions, but whereas for 3-Rh, CO migratory insertion was fast, yielding a carbamoyl carbonyl species, 4-Rh, the stronger Ir-N bond of complex 3-Ir caused the reaction to stop at the CO coordination stage. In contrast, 3-Ir reacted reversibly with CH, forming adduct 5-Ir, which subsequently rearranged irreversibly to [Ir](H)(═C(Me)N(Ph)-) complex 6-Ir, which contains an N-stabilized carbene ligand. Computational studies supported a migratory insertion mechanism, giving first a β-stabilized linear alkyl unit, [Ir]CHCHN(Ph)-, followed by a multistep rearrangement that led to the final product 6-Ir. Both β- and α-H eliminations, as well as their microscopic reverse migratory insertion reactions, were implicated in the alkyl-to-hydride-carbene reorganization. The analogous reaction of 3-Rh with CH originated a complex mixture of products from which only a branched alkyl [Rh]C(H)(Me)N(Ph)- (5-Rh) could be isolated, featuring a β-agostic methyl interaction. Reactions of 3-M with H promoted a catalytic isomerization of the Ap ligand from classical κ-N,N' binding to κ-N plus η-pseudoallyl coordination mode.

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Section: Computational Detailsmentioning

confidence: 99%

Activation of Small Molecules by the Metal–Amido Bond of Rhodium(III) and Iridium(III) (η⁵-C₅Me₅)M-Aminopyridinate Complexes

et al. 2017

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N²‐Selective Autocatalytic Ditriazolylation Reactions of Cyclopropenones and Tropone with N¹‐Sulfonyl‐1,2,3‐triazoles

Jiang

Hao

et al. 2017

Adv Synth Catal

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N2‐Selective autocatalytic ditriazolylation reactions of cyclopropenones and tropone with N1‐sulfonyl‐1,2,3‐triazoles are reported for the first time. In contrast to previous methods for preparing N2‐substituted bis(1,2,3‐triazolyl) compounds, the present reaction achieved ditriazolylation in one step under simple and user‐friendly conditions with a wide substrate scope. A plausible mechanism has been proposed relying on preliminary mechanistic investigations.magnified image

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Mild, Selective Ru‐Catalyzed Deuteration Using D₂O as a Deuterium Source

Eisele

Ullwer

Scholz

et al. 2019

Chemistry A European J

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Am ethodf or the selective deuteration of polyfunctional organic molecules using catalytic amounts of [RuCl 2 (PPh 3 ) 3 ]a nd D 2 Oa sadeuterium source is presented. Throughv ariation of additives like CuI, KOH, and various amounts of zinc powder,o rthogonal chemoselectivities in the deuteration process are observed.M echanistic investigation indicates the presence of different, defined Rucomplexes under the given specific conditions. Scheme1.Activation of the precatalyst [RuCl 2 (PPh 3 ) 3 ]( 1)t hrough additives. Scheme2.Additive-directed chemoselective reductive deuteration of carbonylc ompounds and alkynes.[ a] 16 hreactiont ime.

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Exceedingly Facile PhX Activation (X=Cl, Br, I) with Ruthenium(II): Arresting Kinetics, Autocatalysis, and Mechanisms

Cited by 5 publications

References 25 publications

Activation of Small Molecules by the Metal–Amido Bond of Rhodium(III) and Iridium(III) (η⁵-C₅Me₅)M-Aminopyridinate Complexes

Activation of Small Molecules by the Metal–Amido Bond of Rhodium(III) and Iridium(III) (η⁵-C₅Me₅)M-Aminopyridinate Complexes

N²‐Selective Autocatalytic Ditriazolylation Reactions of Cyclopropenones and Tropone with N¹‐Sulfonyl‐1,2,3‐triazoles

Mild, Selective Ru‐Catalyzed Deuteration Using D₂O as a Deuterium Source

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Exceedingly Facile PhX Activation (X=Cl, Br, I) with Ruthenium(II): Arresting Kinetics, Autocatalysis, and Mechanisms

Cited by 5 publications

References 25 publications

Activation of Small Molecules by the Metal–Amido Bond of Rhodium(III) and Iridium(III) (η5-C5Me5)M-Aminopyridinate Complexes

Activation of Small Molecules by the Metal–Amido Bond of Rhodium(III) and Iridium(III) (η5-C5Me5)M-Aminopyridinate Complexes

N2‐Selective Autocatalytic Ditriazolylation Reactions of Cyclopropenones and Tropone with N1‐Sulfonyl‐1,2,3‐triazoles

Mild, Selective Ru‐Catalyzed Deuteration Using D2O as a Deuterium Source

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Activation of Small Molecules by the Metal–Amido Bond of Rhodium(III) and Iridium(III) (η⁵-C₅Me₅)M-Aminopyridinate Complexes

Activation of Small Molecules by the Metal–Amido Bond of Rhodium(III) and Iridium(III) (η⁵-C₅Me₅)M-Aminopyridinate Complexes

N²‐Selective Autocatalytic Ditriazolylation Reactions of Cyclopropenones and Tropone with N¹‐Sulfonyl‐1,2,3‐triazoles

Mild, Selective Ru‐Catalyzed Deuteration Using D₂O as a Deuterium Source