- Tertiary arsine ligands for the Stille coupling reaction
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The Stille coupling reaction is one of the most important coupling reactions. It is well known that the triphenylarsine ligand can accelerate the reaction rate of Stille coupling. However, other arsine ligands have never been investigated for the Stille c
- Chishiro, Akane,Imoto, Hiroaki,Inaba, Ryoto,Konishi, Masafumi,Naka, Kensuke,Yumura, Takashi
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- The decisive role of ligand metathesis in Au/Pd bimetallic catalysis
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AuClL1/PdCl2L22 cocatalyzed coupling of Ar1X and Ar2SnBu3 is feasible for bulky Ar1, provided that at least one ligand on Pd is not strongly coordinating. This can be
- DelPozo, Juan,Casares, Juan A.,Espinet, Pablo
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supporting information
p. 7246 - 7248
(2013/08/23)
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- η5-Cyclopentadienylpalladium(II) complexes: Synthesis, characterization and use for the vinyl addition polymerization of norbornene and the copolymerization with 5-vinyl-2-norbornene or 5-ethylidene-2-norbornene
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Dinuclear complexes of palladium(II), containing two bridging halogen (Cl or Br) ligands, [NnBu4]2[(X5C 6)2Pd(μ-Cl)2Pd(C6X 5)2] and [(X5C6)(L)Pd(μ-Y) 2Pd(C6X5)(L)] (X = F, Cl; Y = Cl, Br), readily react with cyclopentadienylthallium, C5H5Tl, to give the corresponding air stable half-sandwich, pseudo-trigonal η5- cyclopentadienylpalladium complexes, [NnBu4] [(η5-C5H5)Pd(C6X 5)2] (X = F 1, Cl 2) and (η5-C 5H5)Pd(C6X5)(L) (X = F, L = CNBut 3, PPh3 4, PMe2Ph 5, PEt3 6, AsPh3 7, SbPh3 8; X = Cl, L = PMe2Ph 9, PEt3 10), respectively. With tetraphenylcyclopentadienylthallium, C5Ph4HTl or pentabenzylcyclopentadienylthallium, C 5Bn5Tl (Bn = CH2Ph) the air stable half-sandwich complexes (η5-C5Ph4H) Pd(C6F5)(AsPh3), 12 and (η5- C5Bn5)Pd(C6F5)(AsPh3), 13 are synthesized accordingly. The molecular structures were verified by NMR-spectroscopy, X-ray crystallography (7, 12, 13) and electron impact-mass spectrometry (EI-MS). The precatalysts 4 and 7 can be activated with methylalumoxane (MAO) for the homopolymerization of norbornene (NB) and 5-ethylidene-2-norbornene (ENB) and for the copolymerization of NB with 5-vinyl-2-norbornene (VNB) or ENB with activities of more than 106 gPNB/(molPd·h). The higher activity of 7/MAO over 4/MAO towards NB homopolymerization was reversed when the olefin-substituted VNB or ENB were added. Then, the more strongly bound PPh3 ligand of 4 (versus AsPh3 of 7) can compete with the olefin functionality of VNB or ENB and assume a directing role for the insertion of the ring double bond. As a consequence 4/MAO shows almost the same activity in NB and ENB homopolymerization.
- Blank, Frederik,Vieth, Jana K.,Ruiz, José,Rodríguez, Venancio,Janiak, Christoph
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p. 473 - 487
(2011/02/28)
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- CATIONIC η5-CYCLOPENTADIENYLPALLADIUM(II) COMPLEXES. COMPOUNDS OF TYPE 5-C5H5)L2>PF6 CONTAINING . TERTIARY PHOSPHINES, ARSINES, AND STIBINES. CRYSTAL AND MOLECULAR STRUCTURE OF η5-CYCLOPENTADIENYLBIS(TRIPHENYLSTIBINE)PALLADIUM(II) HEXAFLUOROPHOSPHATE-DICHLOROMETHANE (1/1)
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The complexes 5-C5H5)L2>PF6 have been prepared in high yield from the appropriate complexes and cyclopentadiene in Me2CO in the presence of AgPF6, or with AgNO3 followed by metathesis with NH4PF6.The brighly coloured compounds condudt as uni-univalent electrolytes in Me2CO and CH2Cl2 and have spectroscopic properties consistent with η5 co-ordination of the cyclopentadienyl moiety in solution.The molecular structure of 5-C5H5)(SbPh3)2>PF6*CH2Cl2 has been determined by a single crystal X-ray analysis.The crystals are monoclinic, space group P21/c with a=12.506(6), b=19.002(7), c=18.575(5) Angstoem, β=106.53(3) deg, and Z=4.The structure was solved by heavy-atom methods at 295(1) K and refined by least-squares methods to R=0.051 for 4383 observed reflections.The arrangement of two antimony atoms and the centre of the cyclopentadienyl ring about the palladium atom is approximately trigonal.The co-ordinated cyclopentadienyl moiety shows no significant deviations from planarity.
- Roberts, Nicholas K.,Skelton, Brian W.,White, Allan H.,Wild, Stanley, Bruce
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p. 2093 - 2098
(2007/10/02)
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- Preparation, characterization, and some reactions of tri-tert-butylarsine complexes of platinum(II) and palladium(II) chlorides
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As(t-Bu)3 reacts with platinum(II) chlorides to afford either trans-PtCl2[As(t-Bu)3]2 or the dinuclear complex Pt2(μ-Cl)2Cl2[As(t-Bu)3] 2. With palladium(II) chloride, however, only the dinuclear complex Pd2(μ-Cl)2Cl2[As(t-Bu)3] 2 is formed even in the presence of excess As(t-Bu)3. These complexes undergo substitution and/or bridge-cleavage reactions with CO, py, AsPh3, Cl-, or tertiary phosphines.
- Goel, Ram G.,Ogini, William O.,Srivastava, Ramesh C.
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p. 3611 - 3616
(2008/10/08)
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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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- Photoactivation of Carbonyl Sulphide in Presence of Platinum Metal Ions and Their Complexes
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The photolytic reactions of carbonyl sulphide with ruthenium (II), ruthenium (III), rhodium (I) complexes and with RuCl3*xH2O, RuCl3*3H2O and PdCl2 in the presence of excess of PPh3 and AsPh3 have been investigated.The reaction products have been characterised by elemental analyses, IR spectra and other physicochemical data.In most of the cases the photoactivated reactions show significant differences when compared product-wise with thermally activated reactions.
- Datta, Someswar,Agarwala, U. C.
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p. 1153 - 1155
(2007/10/02)
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