1313-85-5Relevant articles and documents
Cyclopalladation of dimesityl selenide: Synthesis, reactivity, structural characterization, isolation of an intermediate complex with C-H...Pd intra-molecular interaction and computational studies
Kolay, Siddhartha,Wadawale, Amey,Das, Dasarathi,Kisan, Hemanta K.,Sunoj, Raghavan B.,Jain, Vimal K.
supporting information, p. 10828 - 10837 (2013/09/12)
The reaction of dimesityl selenide (Mes2Se) with either PdCl2(PhCN)2 in toluene or PdCl2 in toluene-acetonitrile yields a chloro-bridged binuclear palladium complex, [Pd2Cl2(μ-Cl)2(Mes2Se) 2] (1), whereas with Na2PdCl4 in refluxing ethanol, a cyclometallated palladium complex, [Pd2(μ-Cl) 2{MesSeC6H2(Me2)CH2} 2] (2) is afforded. 2 can also be obtained when 1 is refluxed in ethanol. On treatment with Pb(Epy)2 in dichloromethane, 2 afforded the Epy-bridged binuclear complexes, [Pd2(μ-Epy) 2{MesSeC6H2(Me2)CH2} 2] (3; E = S (3a) or Se (3b)). Treatment of 2 with PPh3 yields a bridge-cleaved monomeric complex, [PdCl{MesSeC6H 2(Me2)CH2}(PPh3)]. The molecular structures of 1-3 were established by X-ray diffraction analyses. All the complexes are dimeric, with the palladium atoms acquiring a distorted square planar configuration. There are intra-molecular C-H...Pd interactions (dM-H: 2.75 A and 3) bond leading to metallation. The optimized geometry of 1 obtained using the DFT(B3LYP) computational method identified a C-H...Pd contact distance of 2.78 A. There are two independent molecules of 2 in the unit cell, which differ slightly in bond lengths, bond angles and torsion angles. The mechanism of formation of the dimeric species 2 is examined using DFT (B3LYP) computations. The Royal Society of Chemistry 2013.
