dc.contributor.author
Scherz, Frederik
dc.contributor.author
Bauer, Markus
dc.contributor.author
Domenianni, Luis I.
dc.contributor.author
Hoyer, Carolin
dc.contributor.author
Schmidt, Jonas
dc.contributor.author
Sarkar, Biprajit
dc.contributor.author
Vöhringer, Peter
dc.contributor.author
Krewald, Vera
dc.date.accessioned
2024-05-15T10:11:42Z
dc.date.available
2024-05-15T10:11:42Z
dc.identifier.uri
https://refubium.fu-berlin.de/handle/fub188/43562
dc.identifier.uri
http://dx.doi.org/10.17169/refubium-43278
dc.description.abstract
Ferrocene and its derivatives have fascinated chemists for more than 70 years, not least due to the analogies with the properties of benzene. Despite these similarities, the obvious difference between benzene and ferrocene is the presence of an iron ion and hence the availability of d-orbitals for properties and reactivity. Phenylnitrene with its rich photochemistry can be considered an analogue of nitrenoferrocene. As with most organic and inorganic nitrenes, nitrenoferrocene can be obtained by irradiating the azide precursor. We study the photophysical and photochemical processes of dinitrogen release from 1,1′-diazidoferrocene to form 1-azido-1′-nitrenoferrocene with UV-pump–mid-IR-probe transient absorption spectroscopy and time-dependent density functional theory calculations including spin–orbit coupling. An intermediate with a bent azide moiety is identified that is pre-organised for dinitrogen release via a low-lying transition state. The photochemical decay paths on the singlet and triplet surfaces including the importance of spin–orbit coupling are discussed. We compare our findings with the processes discussed for photochemical dinitrogen activation and highlight implications for the photochemistry of azides more generally.
en
dc.format.extent
9 Seiten
dc.rights.uri
https://creativecommons.org/licenses/by/4.0/
dc.subject
Ultrafast photogeneration
en
dc.subject
metal–organic nitrene
en
dc.subject
1,1′-diazidoferrocene
en
dc.subject.ddc
500 Naturwissenschaften und Mathematik::540 Chemie::540 Chemie und zugeordnete Wissenschaften
dc.title
Ultrafast photogeneration of a metal–organic nitrene from 1,1′-diazidoferrocene
dc.type
Wissenschaftlicher Artikel
dc.date.updated
2024-05-09T03:00:07Z
dcterms.bibliographicCitation.doi
10.1039/d4sc00883a
dcterms.bibliographicCitation.journaltitle
Chemical Science
dcterms.bibliographicCitation.number
18
dcterms.bibliographicCitation.originalpublishername
The Royal Society of Chemistry
dcterms.bibliographicCitation.pagestart
6707
dcterms.bibliographicCitation.pageend
6715
dcterms.bibliographicCitation.volume
15
dcterms.bibliographicCitation.url
https://doi.org/10.1039/D4SC00883A
refubium.affiliation
Biologie, Chemie, Pharmazie
refubium.affiliation.other
Institut für Chemie und Biochemie
refubium.resourceType.isindependentpub
no
dcterms.accessRights.openaire
open access
dcterms.isPartOf.issn
2041-6520
dcterms.isPartOf.eissn
2041-6539
refubium.resourceType.provider
DeepGreen