Rigid five- and six-membered C,N,N'-bound aryl-, benzyl-, and alkylorganopalladium complexes: sp2 vs. sp3 carbon-hydrogen activation during cyclopalladation and palladium(IV) intermediates in oxidative addition reactions with dihalogens and alkyl halides

Redox-Induced Aromatic C–H Bond Functionalization in Metal Complex Catalysis from the Electrochemical Point of View

“…The ability of Pd(II) to activate C-H bonds through chelation-assisted processes has been known since the 1960s. Nitrogen-containing directing groups were found to promote the insertion of palladium into an ortho-C-H bond, which led to the formation of stable and isolable cyclopalladated complexes from Pd(II) starting material (Scheme 6) [25,[31][32][33][34][35][36][37][38][39][40]. The ability of Pd(II) to activate C-H bonds through chelation-assisted processes has been known since the 1960s.…”

“…The ability of Pd(II) to activate C-H bonds through chelation-assisted processes has been known since the 1960s. Nitrogen-containing directing groups were found to promote the insertion of palladium into an ortho-C-H bond, which led to the formation of stable and isolable cyclopalladated complexes from Pd(II) starting material (Scheme 6) [25,[31][32][33][34][35][36][37][38][39][40]. Despite the large literature devoted to the synthesis of various palladacycles and studies of their reactivity, their redox properties, which are necessary to describe and understand the mechanisms of catalytic reactions involving them, are elucidated only in few works [11,15,24,25,[41][42][43][44].…”

Cyclometalation Using d-Block Transition Metals: Fundamental Aspects and Recent Trends

“…Such species have been detected and isolated. 97,98 Transient decoordination of either a ligand (L or X from A) or a donor site (from B) yields the coordinatively unsaturated complex C as the key intermediate For amines as donor sites (E = NR 2 ), generally, large N-substituents weaken metal coordination substantially. 99 Dimethylamino groups (E = NMe 2 ) have proven to be particularly suitable, 30 while NEt 2 groups coordinate much weaker and higher homologs (e.g.…”

Katalytische Funktionalisierung von C(sp2)‐H‐ und C(sp3)‐H‐Bindungen unter Verwendung von zweizähnigen dirigierenden Gruppen

“…[10] Schema 5. Palladiumkatalysierte Arylierung von C-H-Bindungen durch C-H-Bindungsaktivierung mittels einer zweizähnigen dirigierenden Gruppe.…”

“…Substrate, die zwei potenziell C-H-Funktionalisierung zweizähnigen dirigierenden Gruppen, zu katalytischen Reaktionen zu gelangen. [10] 7. Zusammenfassung und Ausblick Seit der bahnbrechenden Entdeckung von Daugulis 2005 ist die Anwendung zweizähniger dirigierender Gruppen bei der gezielten C-H-Aktivierung intensiv erforscht worden.…”