Non-heme-iron-mediated selective halogenation ofuUnactivated carbon-hydrogen bonds
Oxidation of the iron(II) precursor [(L1)FeIICl2], where L1 is a tetradentate bispidine, with soluble iodosylbenzene (sPhIO) leads to the extremely reactive ferryl oxidant [(L1)(Cl)FeIV=O]+ with a cis disposition of the chlorido and oxido coligands, as observed in non-heme halogenase enzymes. Experi...
Gespeichert in:
| Hauptverfasser: | , , , , , , , , |
|---|---|
| Dokumenttyp: | Article (Journal) |
| Sprache: | Englisch |
| Veröffentlicht: |
2022
|
| In: |
Chemistry - a European journal
Year: 2022, Jahrgang: 28, Heft: 4, Pages: 1-9 |
| ISSN: | 1521-3765 |
| DOI: | 10.1002/chem.202103452 |
| Online-Zugang: | Verlag, kostenfrei, Volltext: https://doi.org/10.1002/chem.202103452 Verlag, kostenfrei, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.202103452 
|
| Verfasserangaben: | Katharina Bleher, Peter Comba, Dieter Faltermeier, Ashutosh Gupta, Marion Kerscher, Saskia Krieg, Bodo Martin, Gunasekaran Velmurugan, and Shuyi Yang |
MARC
| LEADER | 00000caa a2200000 c 4500 | ||
|---|---|---|---|
| 001 | 183035566X | ||
| 003 | DE-627 | ||
| 005 | 20230427151607.0 | ||
| 007 | cr uuu---uuuuu | ||
| 008 | 230104s2022 xx |||||o 00| ||eng c | ||
| 024 | 7 | |a 10.1002/chem.202103452 |2 doi | |
| 035 | |a (DE-627)183035566X | ||
| 035 | |a (DE-599)KXP183035566X | ||
| 035 | |a (OCoLC)1360436521 | ||
| 040 | |a DE-627 |b ger |c DE-627 |e rda | ||
| 041 | |a eng | ||
| 084 | |a 30 |2 sdnb | ||
| 100 | 1 | |a Bleher, Katharina |e VerfasserIn |0 (DE-588)1214903312 |0 (DE-627)1725995948 |4 aut | |
| 245 | 1 | 0 | |a Non-heme-iron-mediated selective halogenation ofuUnactivated carbon-hydrogen bonds |c Katharina Bleher, Peter Comba, Dieter Faltermeier, Ashutosh Gupta, Marion Kerscher, Saskia Krieg, Bodo Martin, Gunasekaran Velmurugan, and Shuyi Yang |
| 264 | 1 | |c 2022 | |
| 300 | |a 9 | ||
| 336 | |a Text |b txt |2 rdacontent | ||
| 337 | |a Computermedien |b c |2 rdamedia | ||
| 338 | |a Online-Ressource |b cr |2 rdacarrier | ||
| 500 | |a Gesehen am 04.01.2023 | ||
| 520 | |a Oxidation of the iron(II) precursor [(L1)FeIICl2], where L1 is a tetradentate bispidine, with soluble iodosylbenzene (sPhIO) leads to the extremely reactive ferryl oxidant [(L1)(Cl)FeIV=O]+ with a cis disposition of the chlorido and oxido coligands, as observed in non-heme halogenase enzymes. Experimental data indicate that, with cyclohexane as substrate, there is selective formation of chlorocyclohexane, the halogenation being initiated by C−H abstraction and the result of a rebound of the ensuing radical to an iron-bound Cl−. The time-resolved formation of the halogenation product indicates that this primarily results from sPhIO oxidation of an initially formed oxido-bridged diiron(III) resting state. The high yield of up to >70 % (stoichiometric reaction) as well as the differing reactivities of free Fe2+ and Fe3+ in comparison with [(L1)FeIICl2] indicate a high complex stability of the bispidine-iron complexes. DFT analysis shows that, due to a large driving force and small triplet-quintet gap, [(L1)(Cl)FeIV=O]+ is the most reactive small-molecule halogenase model, that the FeIII/radical rebound intermediate has a relatively long lifetime (as supported by experimentally observed cage escape), and that this intermediate has, as observed experimentally, a lower energy barrier to the halogenation than the hydroxylation product; this is shown to primarily be due to steric effects. | ||
| 650 | 4 | |a biomimetic coordination chemistry | |
| 650 | 4 | |a C−H activation | |
| 650 | 4 | |a DFT calculations | |
| 650 | 4 | |a non-heme-iron | |
| 650 | 4 | |a reaction mechanism | |
| 700 | 1 | |a Comba, Peter |d 1953- |e VerfasserIn |0 (DE-588)122976843 |0 (DE-627)082271712 |0 (DE-576)160608988 |4 aut | |
| 700 | 1 | |a Faltermeier, Dieter |e VerfasserIn |4 aut | |
| 700 | 1 | |a Gupta, Ashutosh |e VerfasserIn |4 aut | |
| 700 | 1 | |a Kerscher, Marion |e VerfasserIn |0 (DE-588)1074024087 |0 (DE-627)830169598 |0 (DE-576)187074925 |4 aut | |
| 700 | 1 | |a Krieg, Saskia |e VerfasserIn |4 aut | |
| 700 | 1 | |a Martin, Bodo |d 1967- |e VerfasserIn |0 (DE-588)129739294 |0 (DE-627)478573561 |0 (DE-576)189914734 |4 aut | |
| 700 | 1 | |a Velmurugan, Gunasekaran |e VerfasserIn |4 aut | |
| 700 | 1 | |a Yang, Shuyi |e VerfasserIn |4 aut | |
| 773 | 0 | 8 | |i Enthalten in |t Chemistry - a European journal |d Weinheim : Wiley-VCH, 1995 |g 28(2022), 4, Artikel-ID e202103452, Seite 1-9 |h Online-Ressource |w (DE-627)270935193 |w (DE-600)1478547-X |w (DE-576)078707404 |x 1521-3765 |7 nnas |a Non-heme-iron-mediated selective halogenation ofuUnactivated carbon-hydrogen bonds |
| 773 | 1 | 8 | |g volume:28 |g year:2022 |g number:4 |g elocationid:e202103452 |g pages:1-9 |g extent:9 |a Non-heme-iron-mediated selective halogenation ofuUnactivated carbon-hydrogen bonds |
| 856 | 4 | 0 | |u https://doi.org/10.1002/chem.202103452 |x Verlag |x Resolving-System |z kostenfrei |3 Volltext |
| 856 | 4 | 0 | |u https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.202103452 |x Verlag |z kostenfrei |3 Volltext |
| 951 | |a AR | ||
| 992 | |a 20230104 | ||
| 993 | |a Article | ||
| 994 | |a 2022 | ||
| 998 | |g 129739294 |a Martin, Bodo |m 129739294:Martin, Bodo |d 120000 |d 120200 |e 120000PM129739294 |e 120200PM129739294 |k 0/120000/ |k 1/120000/120200/ |p 7 | ||
| 998 | |g 1074024087 |a Kerscher, Marion |m 1074024087:Kerscher, Marion |d 120000 |d 120200 |e 120000PK1074024087 |e 120200PK1074024087 |k 0/120000/ |k 1/120000/120200/ |p 5 | ||
| 998 | |g 122976843 |a Comba, Peter |m 122976843:Comba, Peter |d 120000 |d 120200 |e 120000PC122976843 |e 120200PC122976843 |k 0/120000/ |k 1/120000/120200/ |p 2 | ||
| 998 | |g 1214903312 |a Bleher, Katharina |m 1214903312:Bleher, Katharina |d 120000 |d 120200 |e 120000PB1214903312 |e 120200PB1214903312 |k 0/120000/ |k 1/120000/120200/ |p 1 |x j | ||
| 999 | |a KXP-PPN183035566X |e 4244169407 | ||
| BIB | |a Y | ||
| SER | |a journal | ||
| JSO | |a {"type":{"media":"Online-Ressource","bibl":"article-journal"},"note":["Gesehen am 04.01.2023"],"recId":"183035566X","person":[{"family":"Bleher","display":"Bleher, Katharina","roleDisplay":"VerfasserIn","role":"aut","given":"Katharina"},{"roleDisplay":"VerfasserIn","role":"aut","given":"Peter","display":"Comba, Peter","family":"Comba"},{"display":"Faltermeier, Dieter","role":"aut","roleDisplay":"VerfasserIn","given":"Dieter","family":"Faltermeier"},{"role":"aut","roleDisplay":"VerfasserIn","given":"Ashutosh","display":"Gupta, Ashutosh","family":"Gupta"},{"family":"Kerscher","display":"Kerscher, Marion","roleDisplay":"VerfasserIn","role":"aut","given":"Marion"},{"role":"aut","roleDisplay":"VerfasserIn","given":"Saskia","display":"Krieg, Saskia","family":"Krieg"},{"display":"Martin, Bodo","given":"Bodo","roleDisplay":"VerfasserIn","role":"aut","family":"Martin"},{"family":"Velmurugan","display":"Velmurugan, Gunasekaran","given":"Gunasekaran","roleDisplay":"VerfasserIn","role":"aut"},{"roleDisplay":"VerfasserIn","role":"aut","given":"Shuyi","display":"Yang, Shuyi","family":"Yang"}],"language":["eng"],"name":{"displayForm":["Katharina Bleher, Peter Comba, Dieter Faltermeier, Ashutosh Gupta, Marion Kerscher, Saskia Krieg, Bodo Martin, Gunasekaran Velmurugan, and Shuyi Yang"]},"physDesc":[{"extent":"9 S."}],"id":{"doi":["10.1002/chem.202103452"],"eki":["183035566X"]},"origin":[{"dateIssuedKey":"2022","dateIssuedDisp":"2022"}],"relHost":[{"id":{"zdb":["1478547-X"],"eki":["270935193"],"doi":["10.1002/(ISSN)1521-3765"],"issn":["1521-3765"]},"pubHistory":["1.1995 -"],"type":{"bibl":"periodical","media":"Online-Ressource"},"part":{"pages":"1-9","extent":"9","year":"2022","text":"28(2022), 4, Artikel-ID e202103452, Seite 1-9","issue":"4","volume":"28"},"recId":"270935193","note":["Fortsetzung der Druck-Ausgabe","Gesehen am 27. Februar 2017"],"origin":[{"publisherPlace":"Weinheim","dateIssuedKey":"1995","dateIssuedDisp":"1995-","publisher":"Wiley-VCH"}],"physDesc":[{"extent":"Online-Ressource"}],"disp":"Non-heme-iron-mediated selective halogenation ofuUnactivated carbon-hydrogen bondsChemistry - a European journal","language":["eng"],"title":[{"title":"Chemistry - a European journal","title_sort":"Chemistry - a European journal"}]}],"title":[{"title_sort":"Non-heme-iron-mediated selective halogenation ofuUnactivated carbon-hydrogen bonds","title":"Non-heme-iron-mediated selective halogenation ofuUnactivated carbon-hydrogen bonds"}]} | ||
| SRT | |a BLEHERKATHNONHEMEIRO2022 | ||