2021
DOI: 10.1039/d0cc08236h
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Catalytic hydrogenation enabled by ligand-based storage of hydrogen

Abstract: Biology employs exquisite control over proton, electron, H-atom, or H2 transfer. Similar control in synthetic systems has the potential to facilitate efficient and selective catalysis. Here we report a dihydrazonopyrrole...

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Cited by 21 publications
(33 citation statements)
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“…We reasoned that the previously reported pyrrole-based ligand scaffold t Bu,Tol DHP ( t Bu,Tol DHP = 2,5-bis((2- t -butylhydrazono)( p -tolyl)methyl)-pyrrole, Scheme 1 ), which can donate two electrons and two protons to a substrate, would be an ideal scaffold to demonstrate this principle. 69 Here, we show that the preorganization of protons and electrons on this ligand scaffold allows for the direct formation of an Fe(III)-hydroperoxo intermediate from O 2 , mirroring the type of reactivity and preorganization found in the protein superstructure of biological systems. This Fe(III)-hydroperoxo intermediate has been characterized by a variety of spectroscopic techniques in addition to kinetic and computational analysis.…”
Section: Introductionsupporting
confidence: 54%
“…We reasoned that the previously reported pyrrole-based ligand scaffold t Bu,Tol DHP ( t Bu,Tol DHP = 2,5-bis((2- t -butylhydrazono)( p -tolyl)methyl)-pyrrole, Scheme 1 ), which can donate two electrons and two protons to a substrate, would be an ideal scaffold to demonstrate this principle. 69 Here, we show that the preorganization of protons and electrons on this ligand scaffold allows for the direct formation of an Fe(III)-hydroperoxo intermediate from O 2 , mirroring the type of reactivity and preorganization found in the protein superstructure of biological systems. This Fe(III)-hydroperoxo intermediate has been characterized by a variety of spectroscopic techniques in addition to kinetic and computational analysis.…”
Section: Introductionsupporting
confidence: 54%
“…We reasoned that the previously reported pyrrolebased ligand scaffold tBu,Tol DHP ( tBu,Tol DHP = 2,5-bis((2-tbutylhydrazono)(p-tolyl)methyl)-pyrrole, Scheme 1), which can donate two electrons and two protons to a substrate, would be an ideal scaffold to demonstrate this principle. 69 Here, we show that the preorganization of protons and electrons on this ligand scaffold allows for the direct formation of an Fe(III)-hydroperoxo intermediate from O 2 , mirroring the type of reactivity and preorganization found in the protein superstructure of biological systems. This Fe(III)-hydroperoxo intermediate has been characterized by a variety of spectroscopic techniques in addition to kinetic and computational analysis.…”
Section: ■ Introductionsupporting
confidence: 54%
“…We reasoned that the previously reported pyrrole-based ligand scaffold tBu,Tol DHP ( tBu,Tol DHP = 2,5bis((2-t-butylhydrazono)(p-tolyl)methyl)-pyrrole, Scheme 1), which can donate two electrons and two protons to a substrate, would be an ideal scaffold to demonstrate this principle. 69 Here we show that the preorganization of protons and electrons on this ligand scaffold allows for the direct formation of an Fe(III)-hydroperoxo intermediate from O2, mirroring the type of reactivity and Scheme 1. Metalation of tBu,Tol DHP-H2•2HCl with FeCl2.…”
Section: Enzymaticmentioning
confidence: 55%
“…This presence of a low energy absorbance was previously seen with isolated tBu/Ph,Tol DHP ligand radicals on Ni and Fe centers, further supporting the assignment of 3 with a ligand based radical on tBu,Tol DHP-H • (Scheme 2). 53,69,86…”
Section: Computational Analysis Ofmentioning
confidence: 99%