Mechanistic insights into the reactions of hydride transfer versus hydrogen atom transfer by a trans-dioxoruthenium(<scp>vi</scp>) complex

Dhuri, Sunder N.; Lee, Yong Min; Seo, Mi Sook; Cho, Jaeheung; Narulkar, Dattaprasad D.; Fukuzumi, Shunichi; Nam, Wonwoo

doi:10.1039/c5dt00809c

Cited by 24 publications

(19 citation statements)

References 86 publications

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“…[134,135] Methane monooxygenase [136] operates with large KIEs and has served as inspiration for functional synthetic model complexes. Synthetic inorganic iron heme [45,50,[137][138][139][140] and nonheme [44,49,[141][142][143] compounds, along with other metal oxo complexes [51,52,[144][145][146][147][148][149][150][151][152] , have been found to activate CÀ H bonds with large isotope effects, which are often ascribed to tunneling. Catalytic CÀ H amination by an iron imido complex, and stoichiometric CÀ H amination by a diruthenium nitride site in a metal-organic framework (MOF), have been reported and attributed to tunneling.…”

Section: Cà H Abstraction By Metal-oxo Complexesmentioning

confidence: 99%

Large Isotope Effects in Organometallic Chemistry

Truong

Miller

Maria

et al. 2021

Chemistry A European J

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The kinetic isotope effect (KIE) is key to understanding reaction mechanisms in many areas of chemistry and chemical biology, including organometallic chemistry. This ratio of rate constants, k H /k D , typically falls between 1-7. However, KIEs up to 105 have been reported, and can even be so large that reactivity with deuterium is unobserved. We collect here examples of large KIEs across organometallic chemistry, in catalytic and stoichiometric reactions, along with their mechanistic interpretations. Large KIEs occur in proton transfer reactions such as protonation of organo-metallic complexes and clusters, protonolysis of metal-carbon bonds, and dihydrogen reactivity. CÀ H activation reactions with large KIEs occur with late and early transition metals, photogenerated intermediates, and abstraction by metal-oxo complexes. We categorize the mechanistic interpretations of large KIEs into the following three types: (a) proton tunneling, (b) compound effects from multiple steps, and (c) semiclassical effects on a single step. This comprehensive collection of large KIEs in organometallics provides context for future mechanistic interpretation.

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Section: Cà H Abstraction By Metal-oxo Complexesmentioning

confidence: 99%

Large Isotope Effects in Organometallic Chemistry

Truong

Miller

Maria

et al. 2021

Chemistry A European J

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“…We began our analysis by compiling an extensive data set of second order rate constants (k2) for the oxidation of 9,10dihydroanthracene (DHA) by 28 well-characterized metal oxo complexes. 12,13,15,17,[32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47] This diverse data set comprises complexes of five different transition metals, tetragonal and trigonal geometries, spin multiplicities from 1 to 5, charges from −1 to +3, and d-electron counts from 0 to 6. We manually divided the data set into a training set of seventeen metal oxo complexes and a test set of eleven metal oxo complexes such that each set had a diverse mix of species.…”

Section: Resultsmentioning

confidence: 99%

“…This includes successful extrapolation to the reaction barriers for Cr IV and Ru VI oxo examples. 40,41 Nonetheless, several metal oxo complexes (boxed in the figure) deserve further discussion.…”

Section: Resultsmentioning

confidence: 99%

Statistical Analysis of C–H Activation by Transition Metal Oxo Species Supports Thermodynamic Control Over Reactivity

Schneider¹,

Goetz²,

Anderson

2020

Preprint

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Transition metal oxo species are key intermediates for the activation of strong C‒H bonds. As such, there has been interest in understanding which structural or electronic parameters of metal oxo complexes determine their reactivity. Factors such as ground state thermodynamics, spin state, steric environment, oxygen radical character, and asynchronicity have all been cited as key contributors, yet there is no consensus on when each of these parameters is significant or the relative magnitude of their effects. Herein, we present a thorough statistical analysis of parameters that have been proposed to influence transition metal oxo mediated C‒H activation. We used density functional theory (DFT) to compute parameters for transition metal oxo complexes and analyzed their ability to explain and predict an extensive data set of experimentally determined reaction barriers. We found that, in general, only thermodynamic parameters related to the free energy of hydrogen atom, proton, and electron transfer play a statistically significant role.

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“…Acridane derivatives have potent biological activity consisting of HIV reverse transcriptase inhibitory [17] and neuroleptic activity [18], and activation of K2P potassium channels [19]. Moreover, acridanes have been utilized as host materials in OLEDs [20], chemiluminescent sensors in immunoassays [21], as molecular motors [22] and NADH analogues in hydride transfer reactions [23].…”

Section: Introductionmentioning

confidence: 99%

[1,5]-Hydride Shift-Cyclization versus C(sp2)-H Functionalization in the Knoevenagel-Cyclization Domino Reactions of 1,4- and 1,5-Benzoxazepines

et al. 2020

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Domino cyclization reactions of N-aryl-1,4- and 1,5-benzoxazepine derivatives involving [1,5]-hydride shift or C(sp2)-H functionalization were investigated. Neuroprotective and acetylcholinesterase activities of the products were studied. Domino Knoevenagel-[1,5]-hydride shift-cyclization reaction of N-aryl-1,4-benzoxazepine derivatives with 1,3-dicarbonyl reagents having active methylene group afforded the 1,2,8,9-tetrahydro-7bH-quinolino [1,2-d][1,4]benzoxazepine scaffold with different substitution pattern. The C(sp3)-H activation step of the tertiary amine moiety occurred with complete regioselectivity and the 6-endo cyclization took place in a complete diastereoselective manner. In two cases, the enantiomers of the chiral condensed new 1,4-benzoxazepine systems were separated by chiral HPLC, HPLC-ECD spectra were recorded, and absolute configurations were determined by time-dependent density functional theory- electronic circular dichroism (TDDFT-ECD) calculations. In contrast, the analogue reaction of the regioisomeric N-aryl-1,5-benzoxazepine derivative did not follow the above mechanism but instead the Knoevenagel intermediate reacted in an SEAr reaction [C(sp2)-H functionalization] resulting in a condensed acridane derivative. The AChE inhibitory assays of the new derivatives revealed that the acridane derivative had a 6.98 μM IC50 value.

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Mechanistic insights into the reactions of hydride transfer versus hydrogen atom transfer by a trans-dioxoruthenium(vi) complex

Cited by 24 publications

References 86 publications

Large Isotope Effects in Organometallic Chemistry

Large Isotope Effects in Organometallic Chemistry

Statistical Analysis of C–H Activation by Transition Metal Oxo Species Supports Thermodynamic Control Over Reactivity

[1,5]-Hydride Shift-Cyclization versus C(sp2)-H Functionalization in the Knoevenagel-Cyclization Domino Reactions of 1,4- and 1,5-Benzoxazepines

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