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Aminomethylations of electron-deficient compounds: bringing iron photoredox catalysis into play
Lund Univ, Ctr Anal & Synth CAS, Dept Chem, SE-22100 Lund, Sweden..
Lund Univ, Ctr Anal & Synth CAS, Dept Chem, SE-22100 Lund, Sweden..
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.ORCID iD: 0000-0001-9975-6577
Lund Univ, Ctr Anal & Synth CAS, Dept Chem, SE-22100 Lund, Sweden..
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2024 (English)In: Chemical Science, ISSN 2041-6520, E-ISSN 2041-6539, Vol. 15, no 30, p. 12077-12085Article in journal (Refereed) Published
Abstract [en]

The α-functionalisation of N-containing compounds is an area of broad interest in synthetic chemistry due to their presence in biologically active substances among others. Visible light-induced generation of nucleophilic α-aminoalkyl radicals as reactive intermediates that can be trapped by electron-deficient alkenes presents an attractive and mild approach to achieve said functionalisation. In this work, [Fe(III)(phtmeimb)2]PF6 (phtmeimb = phenyl(tris(3-methylimidazol-2-ylidene))borate), an N-heterocyclic carbene (NHC) complex based on Earth-abundant iron, was used as photoredox catalyst to efficiently drive the formation of α-aminoalkyl radicals from a range of different α-trimethylsilylamines and their subsequent addition to a number of electron-deficient alkenes under green light irradiation. Mechanistic investigations elucidated the different reaction steps of the complete photocatalytic cycle. In terms of yields and substrate scope, we show that [Fe(III)(phtmeimb)2]PF6 can compete with noble metal photoredox catalysts, for instance outcompeting archetypal [Ru(bpy)3]Cl2 under comparable reaction conditions, illustrating that iron photocatalysts can efficiently facilitate photoredox reactions of synthetic value.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2024. Vol. 15, no 30, p. 12077-12085
National Category
Organic Chemistry Atom and Molecular Physics and Optics
Identifiers
URN: urn:nbn:se:uu:diva-540961DOI: 10.1039/d4sc02612hISI: 001261895400001PubMedID: 39092117OAI: oai:DiVA.org:uu-540961DiVA, id: diva2:1908306
Part of project
Photochemistry of iron carbene complexes, Swedish Research Council
Funder
Swedish Foundation for Strategic Research, EM16-0067Knut and Alice Wallenberg Foundation, 2018.0074Swedish Research Council, 2020-05058Swedish Research Council, 2020-03207Swedish Energy Agency, P48747-1LMK StiftelsenSten K Johnson FoundationAvailable from: 2024-10-25 Created: 2024-10-25 Last updated: 2024-12-07Bibliographically approved
In thesis
1. Ferrous and Ferric N-Heterocyclic Carbene Complexes: Characterization and Applications in Photoredox Catalysis
Open this publication in new window or tab >>Ferrous and Ferric N-Heterocyclic Carbene Complexes: Characterization and Applications in Photoredox Catalysis
2025 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Iron complexes are emerging as favourable substitutes to noble metal complexes as photocatalysts due to iron being earth-abundant and inexpensive. Much of the recent progress has been enabled by the strong electron-donating character of N-heterocyclic carbene (NHC) ligands that strongly destabilizes metal-centred (MC) states of FeNHC complexes and thereby greatly extends the lifetimes of their charge transfer (CT) states that are otherwise rapidly deactivated via low-lying MC states.

The first part of this thesis successfully employed FeNHC complexes in different photoredox catalysis (PRC) reactions and an example of high-turnover catalytic hydrogen production. The latter was accomplished with the benchmark ferric bis-tridentate scorpionate complex [FeIII(phtmeimb)2]+ (phtmeimb = phenyl(tris(3-methylimidazol-1-ylidene))borate) which has a 2LMCT state lifetime of two nanoseconds and excellent photostability. It was further employed in two PRC reactions that yielded synthetically-useful organic compounds, where fast and efficient reductive quenching of the 2LMCT state by various amine donors with cage escape yields between 2 and 22 % were observed. A tris-bidentate complex with favourable excited-state (ES) redox properties and lifetimes in both oxidation states, [FeII,III(btz)3]2+,3+ (btz = 3,3’-dimethyl-1,1’-bis(p-tolyl)-4,4’-bis(1,2,3-triazol-5-ylidene)), was employed in a two-photon PRC reaction utilizing both oxidative and reductive quenching steps, making the PRC reaction overall more efficient. 

The second part of this thesis describes the electrochemical and photophysical characterization of novel FeNHC complexes with three different motifs in view of their potential suitability as photocatalysts. (i) For a series of ferric bis-tridentate complexes with cyclometalating ligands, not only were their emissive 2LMCT states with lifetimes of hundreds of picoseconds approaching values previously obtained with the [FeIII(phtmeimb)2]+ motif, their electrochemical and ES properties were more tunable by substituent effects. (ii) For the (NHC)4(bpy)2 bis-tridentate complexes [Fe(btz)2bpy]2+,3+ (bpy = 2,2'-bipyridyl) and [Fe(btz)2mbpy]2+,3+ (mbpy = 4,4'-dimethyl-2,2'-bipyridyl), both ferrous and ferric analogues offered insufficient ES lifetimes on the order of ten ps. The ferrous mbpy variant featured however a more long-lived, presumably MC state that deserves further characterization, also in regard to its potential reactivity. (iii) For the ferrous analogue of [FeIII(phtmeimb)2]+, the strikingly-short picosecond 3MLCT state lifetime concludes that even the phtmeimb- ligand with superior σ-donating ability cannot sufficiently prevent the relatively high-energy 3MLCT state from rapid deactivation. 

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2025. p. 156
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 2482
Keywords
Iron, Earth-Abundant, N-Heterocyclic Carbene, Photoredox Catalysis, Excited State Electron Transfer, Characterization, Photophysics
National Category
Physical Chemistry
Research subject
Chemistry with specialization in Physical Chemistry
Identifiers
urn:nbn:se:uu:diva-544629 (URN)978-91-513-2331-2 (ISBN)
Public defence
2025-02-06, Polhemsalen, Room 10134, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 13:00 (English)
Opponent
Supervisors
Available from: 2025-01-15 Created: 2024-12-07 Last updated: 2025-01-15

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Johnson, Catherine E.Lomoth, Reiner

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