31387-03-8Relevant academic research and scientific papers
Organo palladium(II) complexes with PdC4 coordination: Phenylethinyl- and methylphenylethinylcomplexes
Walther, Dirk,Lamm, Katja,Goerls, Helmar
, p. 1187 - 1195 (2009/12/26)
Tetrakis(p-tolyl)oxalamidinato-bis[acetylacetonatopalladium(II)] ([Pd 2(acac)2(oxam)]) reacted with Li-C=C-C6H5 in THF with formation of [Pd(C=C-C6H5)4Li 2(thf)4] (la). Reaction of [Pd2(acac) 2(oxam)] with a mixture of 6 equiv. Li-C=C-C6H5 and 2 equiv. LiCH3 resulted in the formation of [Pd(CH 3)(C= C-C6H5)3Li2(thf) 4] (2), and the dimeric complex [Pd2(CH3) 4(C=C-C6H5)4Li4(thi) 6] (3) was isolated upon reaction of [Pd2(acac) 2(oxam)] with a mixture of 4 equiv. Li-C=C-C6H5 and 4 equiv. LiCH3. 1-3 are extremely reactive compounds, which were isolated as white needles in good yields (60-90 %). They were fully characterized by IR, 1H-, 13C-, 7Li-NMR spectroscopy, and by X-ray crystallography of single crystals. In these compounds Li ions are bonded to the two carbon atoms of the alkinyl ligand. la reacted with. Pd(PPh3)4 in the presence of oxygen, to form the already known complexes trans-[Pd(C=C-C6H5) 2(PPh3)2] and [Pd(η2-O 2)(PPh3)2]. In addition, la is an active catalyst for the Heck coupling reaction, but less active in the catalytic Sonogashira reaction.
Palladium-catalyzed oxidative carbonylation of 1-alkynes into 2-alkynoates with molecular oxygen as oxidant
Izawa, Yusuke,Shimizu, Isao,Yamamoto, Akio
, p. 2033 - 2045 (2007/10/03)
A new preparative method to produce alkyl 2-alkynoates from 1-alkynes in alcohol under atmospheric pressure of CO at room temperature was developed with palladium-phosphine catalysts, using molecular oxygen as an oxidant. On the basis of the behavior of model complexes such as methoxycarbonylpalladium and alkynylpalladium complexes, we propose a mechanism accounting for the catalytic carbonylation of alkynes through an intermediate having the both methoxycarbonyl and alkynyl ligands that liberates methyl 2-alkynoates and a Pd(0) species on reductive elimination. The oxidation of Pd(0) to Pd(II) species in the presence of a halide ion was confirmed to proceed cleanly with molecular oxygen as the oxidant. On the basis of the findings on homogeneous catalysts, a heterogeneous catalytic system using Pd/C has also been developed.
Synthesis, characterisation and optical properties of symmetrical and unsymmetrical Pt(II) and Pd(II) bis-acetylides. Crystal structure of trans-[Pt(PPh3)2(CC-C6H5)(CC-C 6H4NO2)]
D'Amato,Furlani,Colapietro,Portalone,Casalboni,Falconieri,Russo
, p. 13 - 22 (2007/10/03)
Symmetric trans-[Pt(PPh3)2(CCR)2] and unsymmetrical trans-[Pt(PPh3)2Cl(CCR)], (R=C6H4-pNO2, C6H4-pOCH3), Pt(II) acetylides were prepar
