- Organo palladium(II) complexes with PdC4 coordination: Phenylethinyl- and methylphenylethinylcomplexes
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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.
- Walther, Dirk,Lamm, Katja,Goerls, Helmar
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- Structures of transition states in metal-mediated O2-activation reactions
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(Chemical Equation Presented) Kinetic isotope effects (KIEs) have been used to probe the mechanism of the binding of O2 to classic inorganic compounds. The intermolecular 18O KIEs decrease with increasing rate constants, and the corr
- Lanci, Michael P.,Brinkley, David W.,Stone, Kristie L.,Smirnov, Valeriy V.,Roth, Justine P.
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p. 7273 - 7276
(2007/10/03)
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- Preparation and reactions of bis(triphenylphosphine)palladium(0)
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The two-coordinate palladium complex, (Ph3P)2Pd, is succesfully prepared by the reaction of 3-allyl)Pd(PPh3)2>+ PF6- with Ph2MeSiLi.The complex has been characterized by Ir, 1H NMR, 13C NMR, 31P NMR, and UV spectroscopy
- Urata, Hisao,Suzuki, Hiroharu,Moro-oka, Yoshihiko,Ikawa, Tsuneo
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p. 235 - 244
(2007/10/02)
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- Reactions of Carbonyl Sulphide with Palladium Compounds
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The reactions of carbonyl sulphide (COS) with PdCl2 (in dimethyl sulphoxide), Pd(PPh3)4, Pd(PPh3)2O2 and with PdCl2 in the presence or absence of PPh3 and AsPh3 have been investigated.The reaction products have been characterised and their reactions with PPh3, AsPh3 and SbPh3 or other small molecules have also been examined.The products have been characterised by elemental analyses, infrared spectra, conductivity measurements, magnetic moments and molecular weight measurements (wherever possible).In most of the cases COS forms molecular complexes.However, in some cases, it forms SPPh3 complexes.Reactions of the molecular COS complexes with other small molecules result in the replacement of COS.
- Datta, Someswar,Agarwala, U. C.
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p. 1190 - 1195
(2007/10/02)
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