E-viri
Recenzirano
-
Mao, Weiqing; Zhang, Zihan; Fehn, Dominik; Jannuzzi, Sergio A. V.; Heinemann, Frank W.; Scheurer, Andreas; van Gastel, Maurice; DeBeer, Serena; Munz, Dominik; Meyer, Karsten
Journal of the American Chemical Society, 06/2023, Letnik: 145, Številka: 25Journal Article
The synthesis, characterization, and reactivity of a series of cobalt terminal imido complexes supported by an N-anchored tripodal tris(carbene) chelate is described, including a Co-supported singlet nitrene. Reaction of the CoI precursor (TIMMNmes)CoI(PF6) (TIMMNmes = tris-2-(3-mesityl-imidazolin-2-ylidene)-methylamine) with p-methoxyphenyl azide yields a CoIII imide (TIMMNmes)CoIII(NAnisole)(PF6) (1). Treatment of 1 with 1 equiv of FeCp2(PF6) at −35 °C affords a formal CoIV imido complex (TIMMNmes)Co(NAnisole)(PF6)2 (2), which features a bent Co–N(imido)–C(Anisole) linkage. Subsequent one-electron oxidation of 2 with 1 equiv of AgPF6 provides access to the tricationic cobalt imido complex (TIMMNmes)Co(NAnisole)(PF6)3 (3). All complexes were fully characterized, including single-crystal X-ray diffraction (SC-XRD) analyses, infrared (IR) vibrational, ultraviolet/visible (UV/vis) electronic absorption, multinuclear NMR, X-band electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), and high-energy-resolution fluorescence-detected X-ray absorption spectroscopy (HERFD XAS). Quantum chemical calculations provide additional insight into the electronic structures of all compounds. The dicationic CoIV imido complex 2 exhibits a doublet ground state with considerable imidyl character as a result of covalent Co–NAnisole bonding. At room temperature, 2 readily converts to a CoII amine complex involving intramolecular C–H bond amination. Electronically, tricationic complex 3 can be understood as a singlet nitrene bound to CoIII with significant CoIV imidyl radical character. Verifying the pronounced electrophilicity, nucleophiles such as H2O and t BuNH2 add to 3analogous to the parent free nitrenein the para position of the aromatic substituent, thus, clearly corroborating singlet nitrene-type reactivity.
![loading ... loading ...](themes/default/img/ajax-loading.gif)
Vnos na polico
Trajna povezava
- URL:
Faktor vpliva
Dostop do baze podatkov JCR je dovoljen samo uporabnikom iz Slovenije. Vaš trenutni IP-naslov ni na seznamu dovoljenih za dostop, zato je potrebna avtentikacija z ustreznim računom AAI.
Leto | Faktor vpliva | Izdaja | Kategorija | Razvrstitev | ||||
---|---|---|---|---|---|---|---|---|
JCR | SNIP | JCR | SNIP | JCR | SNIP | JCR | SNIP |
Baze podatkov, v katerih je revija indeksirana
Ime baze podatkov | Področje | Leto |
---|
Povezave do osebnih bibliografij avtorjev | Povezave do podatkov o raziskovalcih v sistemu SICRIS |
---|
Vir: Osebne bibliografije
in: SICRIS
To gradivo vam je dostopno v celotnem besedilu. Če kljub temu želite naročiti gradivo, kliknite gumb Nadaljuj.