1536428-13-3Relevant academic research and scientific papers
Structural and theoretical studies of mono and di-insertion of symmetric alkynes into the Pd-C σ bond of cyclopalladated secondary (tert-butyl and ethyl) benzylamines
Karami, Kazem,Hosseini-Kharat, Mahboubeh,Rizzoli, Corrado,Tavakol, Hossein,Lipkowski, Janusz
, p. 152 - 160 (2014)
The reactivity of the dinuclear cyclopalladated complexes derived from secondary benzylamines, [Pd2{(C,N)-C6H4CH 2NH(R)}2(μ-X)2] [X = Br, R = t-Bu (1a); X = Cl, R = t-Bu (1b); X = Cl, R = Et (1c)] is reported. 1a reacted with dimethyl acetylenedicarboxylate (DMAD) to yield the mono-inserted complex [Pd 2{(C,N)-C(CO2Me)C(CO2Me)C6H 4CH2NH(t-Bu)}2(μ-Br)2] (2a). 1a, 1b and 1c reacted with (R′)CC(R′) (R′ = CO2Me, Ph) to give [Pd{(C,N) C(R′)C(R′)C(R′)C(R′)C 6H4CH2NH(R)}X] [X = Br, R = t-Bu, R′ = CO2Me (3a); X = Cl, R = t-Bu, R′ = Ph (2b); X = Cl, R = Et, R′ = Ph (2c)] through a double insertion of the alkyne into the Pd-C σ bond. 2c also reacts with Ag(CF3SO3) and pyridine to give mononuclear cationic complex [Pd{(C,N)-C(Ph)C(Ph)C(Ph)C(Ph)}C 6H4CH2NH(Et)(py)]CF3SO3 (3c). The crystal structures of di-inserted complexes 2b, 2c and 3c have been determined by X-ray diffraction studies. Their molecular structures showed that the conformation of the CC double bonds within the butadienyl group attached to the aromatic ring was trans-cis. Density functional theory (DFT) calculations also indicated that this arrangement is more stable than other possible conformations.
