Searching for New Four‐membered Palladacycles Derived from Anilines: Influence of the N‐Substituents in the Reaction Outcome
Year: 2025
Type: article
Abstract: The reactions of iodoanilines IC6H4NRR′‐2 with [Pd(PPh3)4] gave complexes [Pd(C6H4NRR′‐2}I(PPh3)2] [R=H, R’=H (1 a), Me (1 b); R=R’=Me (1 c)] while a mixture of 1 a, and the dimeric [Pd{μ‐C,N‐C6H4NH2‐2)I(PPh3)]2 (2 a) was obtained when the appropriate iodoaniline was reacted with [Pd(dba)2] (dba=dibenzylideneacetone) and 1 equiv. of PPh3. The phosphonium salts [Ph3PC6H4NRMe‐2]OTf [R=H (3 b), Me (3 c)] formed upon reacting complexes 1 b,c with TlOTf (OTf=CF3SO3). Complexes of the type [Pd(C6H4NRR′‐2}I(N N)] (4) were obtained from the reaction of [Pd(dba)2] with the appropriate iodoaniline and a N N bidentate ligand (N N=4,4′‐di‐tert‐butyl‐2,2′‐bipyridine or N,N,N′,N′‐tetramethylethylenediamine). Complexes 4 reacted with TlOTf and PPh3 or XyNC (Xy=C4H4Me2‐2,6) to give [Pd(C6H4NRR′‐2)(N N)(PPh3)]OTf (5) or [Pd{C,N‐C(=NHXy)C6H4NRR′‐2)(N N)]OTf (6), respectively. In the absence of any added ligand, the reactions of complexes 4 with TlOTf produced the dimeric complexes [Pd{μ‐C,N‐C6H4NHR‐2)(N N)]2(OTf)2 (7) or the four‐membered palladacycles [Pd(κ2‐C6H4NMe2‐2)(N N)]OTf (8), depending on the substitution degree of the aniline reagent.
Institution: Universidad de Murcia
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,050
Award: G6719864149
OpenAlex ID: W4407106884