279683-88-4Relevant academic research and scientific papers
The synthesis of palladacyclopentadienyl derivatives from rigid bis-alkynes and their use as precursors in the synthesis of fluoroanthene-like cycles under mild conditions. A reactivity investigation
Canovese, Luciano,Visentin, Fabiano,Chessa, Gavino,Uguagliati, Paolo,Santo, Claudio,Maini, Lucia
, p. 2342 - 2345 (2008/01/27)
The palladium(0) derivatives of the type [Pd(η2-ol)(LL′)] (2) (ol = dmfu: dimethylfumarate (a), fn: fumaronitrile (b), tmetc: tetramethylethylenetetracarboxylate (c), LL′ = HNSPh: 2-(phenylthiomethyl)-pyridine (A), BiPy: 2,2′-bipyridyl (B), DPPE: bis-diphenylphosphinoethane (C)) were reacted in CH2Cl2 with 1,8-bis(methylpropynoate)naphthalene (1) and 2,2′-bis(methylpropynoate)biphenyl (1′). At variance with the flexible 1′ derivative, the rigid bis-alkyne 1 reacts smoothly to give the corresponding cyclopalladate complexes [PdC4(COOMe)2(Ph)2(LL′)] (3). The rates of reaction were determined and the X-ray diffraction structure of the complex [PdC4(COOMe)2(Ph)2(HNSPh )] (3A) is reported. The reactivity of the complexes [PdC4(COOMe)2(Ph)2(LL′)] (LL′ = HNSPh (3A), BiPy (3B), DPPE (3C)) was studied by reacting these complexes with fn and tetracyanoethylene (tcne), respectively. The ensuing fluoroanthene-like compounds were fully characterized.
The formation of a metallacycloheptadienyl intermediate in the reaction of palladacyclopentadienyl derivatives with tetracyanoethylene
Canovese, Luciano,Visentin, Fabiano,Santo, Claudio
, p. 4187 - 4192 (2008/02/10)
The palladium(II) derivatives of the type 1 [Pd(LL′)(C4R1R2R3R4)] (LL′ = HNSPh:2-(phenylthiomethyl)-pyridine (A), BiPy: 2,2′-bipyridyl (B), DPPE: bis-diphenylphosphinoethane (C), NEOC: neocuproine (2,
Synthesis, characterization and X-ray structural determination of palladium(0)-olefin complexes containing pyridin-thioethers as ancillary ligands. Equilibria and rates of olefin and ligand exchange
Canovese, Luciano,Visentin, Fabiano,Chessa, Gavino,Uguagliati, Paolo,Dolmella, Alessandro
, p. 1 - 15 (2007/10/03)
The synthesis of Pd(0)-olefin complexes with pyridin-thioether ligands R′N-SR is reported. X-ray structure determinations of selected species are described. The dynamic behavior was studied by variable-temperature 1H-NMR spectrometry. Equilibrium constants for olefin and chelate ligand exchange were determined by UV-vis spectrophotometry in chloroform at 25°C. The following metal-olefin stability order was observed: tetramethylethylenetetracarboxylate (tmetc)≈naphthoquinone (nq)a similar extent, as found in similar Pd(II) complexes. When the entering olefin is tmetc, the approach to equilibrium is slow so that both second-order rate constants k2 and k-2 could be determined along with their activation parameters for the reversible reaction of [Pd(η2-nq)(HN-SiPr)] with tmetc. The results indicate an associative mechanism to be operative in these olefin exchange processes.
