A platinum(ii) metallonitrene with a triplet ground state

Metallonitrenes (M-N) are complexes with a subvalent atomic nitrogen ligand that have been proposed as key reactive intermediates in nitrogen atom transfer reactions. However, in contrast to the common classes of nitride complexes (M equivalent to N) and organic nitrenes (R-N), structurally and spec...

Celý popis

Uloženo v:
Podrobná bibliografie
Vydáno v:Nature chemistry Ročník 12; číslo 11; s. 1054 - 1059
Hlavní autoři: Sun, Jian, Abbenseth, Josh, Verplancke, Hendrik, Diefenbach, Martin, de Bruin, Bas, Hunger, David, Wuertele, Christian, van Slageren, Joris, Holthausen, Max C., Schneider, Sven
Médium: Journal Article
Jazyk:angličtina
Vydáno: BERLIN NATURE PORTFOLIO 01.11.2020
Nature Publishing Group
Témata:
Aldehydes
Chemical bonds
Chemistry
Chemistry, Multidisciplinary
Computer applications
Crystallography
Intermediates
Isocyanates
Ligands
Nitrogen
Organic compounds
Photolysis
Physical Sciences
Platinum
Reactive nitrogen species
Reactivity
Science & Technology
COMPLEX
ACTIVATION
SINGLE
NITRIDO
REACTIVITY
C-H FUNCTIONALIZATION
PHOTOLYSIS
ISSN:1755-4330, 1755-4349, 1755-4349
On-line přístup:Získat plný text
Tagy: Přidat tag
Žádné tagy, Buďte první, kdo vytvoří štítek k tomuto záznamu!
Popis
Shrnutí:Metallonitrenes (M-N) are complexes with a subvalent atomic nitrogen ligand that have been proposed as key reactive intermediates in nitrogen atom transfer reactions. However, in contrast to the common classes of nitride complexes (M equivalent to N) and organic nitrenes (R-N), structurally and spectroscopically well defined 'authentic' metallonitrenes with a monovalent atomic nitrogen ligand remain elusive. Here we report that the photolysis of a platinum(ii) pincer azide complex enabled the crystallographic, spectroscopic, magnetic and computational characterization of a metallonitrene that is best described as a singly bonded atomic nitrogen diradical ligand bound to platinum(ii). The photoproduct exhibits selective C-H, B-H and B-C nitrogen atom insertion reactivity. Despite the subvalent metallonitrene character, mechanistic analysis for aldehyde C-H amidation shows nucleophilic reactivity of the N-diradical ligand. Ambiphilic reactivity of the metallonitrene is indicated by reactions with CO and PMe(3)to form isocyanate and phosphoraneiminato platinum(ii) complexes, respectively. Transient metallonitrenes (M-N) have been proposed as key intermediates in nitrogen atom transfer reactions, but well-defined examples have remained elusive. Now, a platinum complex with an atomic nitrogen ligand, best described as a subvalent nitrogen diradical singly bonded to a platinum(ii) ion (Pt-N), has been isolated and shows ambiphilic reactivity.
Bibliografie:European Research Council (ERC)
ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 14
content type line 23
ISSN:1755-4330
1755-4349
1755-4349
DOI:10.1038/s41557-020-0522-4