- A Polystyrene-Cross-Linking Tricyclohexylphosphine: Synthesis, Characterization and Applications to Pd-Catalyzed Cross-Coupling Reactions of Aryl Chlorides
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A polystyrene-cross-linking tricyclohexylphosphine (PS-TCP) was synthesized through radical emulsion polymerization of 4-tert-butylstyrene as a monomer and tris(trans-4-styrylcyclohexyl)phosphine as a threefold cross-linker. The PS-TCP showed enhanced ligand performance compared to the corresponding polystyrene-triphenylphosphine hybrid PS-TPP and tricyclohexylphosphine in Pd-catalyzed Suzuki–Miyaura and Buchwald–Hartwig reactions of aryl chlorides.
- Arashima, Junya,Iwai, Tomohiro,Sawamura, Masaya
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supporting information
p. 411 - 415
(2019/02/03)
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- Oxidative Mechanochemistry: Direct, Room-Temperature, Solvent-Free Conversion of Palladium and Gold Metals into Soluble Salts and Coordination Complexes
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Noble metals are valued, critical elements whose chemical activation or recycling is challenging, and traditionally requires high temperatures, strong acids or bases, or aggressive complexation agents. By using elementary palladium and gold, demonstrated here is the use of mechanochemistry for noble-metal activation and recycling by mild, clean, solvent-free, and room-temperature chemistry. The process leads to direct, efficient, one-pot conversion of the metals, including spent catalysts, into either simple water-soluble salts or metal–organic catalysts.
- Do, Jean-Louis,Tan, Davin,Fri??i?, Tomislav
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supporting information
p. 2667 - 2671
(2018/02/06)
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- Structural studies of PdCl2L2 complexes with fluorinated phosphines, phosphites, and phosphinites as precursors of benzyl bromide carbonylation catalysts, and and X-ray crystal structure of cis-PdCl2[PPh2 (OEt)]2
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PdCl2L2-type complexes with phosphines (L = PPhx(C6F5)3-x (x = 0-3)), phosphites (L = P(OMe)3, P(OPh)3, P(OEt)3), and phosphinites (L = PPh2 (OC6F5), PPh2(O-3,5-F2 C6H3), PPh2(OEt), PPh2 (O-n-Bu), PPh2(O-t-Bu)) were synthesized and characterized by UV-vis and 31P NMR methods. PdCl2L2 complexes with less sterically demanding phosphines (Θ 2[PPh2(OEt)]2. These complexes react with CO in the presence of NEt3 forming Pd(CO)xLy (x + y = 4) type carbonyls characterized by IR spectra. All PdCl2L2 complexes studied are active as precursors of benzyl bromide carbonylation catalysts at 40°C and 1 atm CO; however, the activity of the cis isomers is higher than that of the trans isomers. The highest yields of the carbonylation product, phenylacetic acid methyl ester, were obtained using cis-PdCl2[P(OMe)3]2 (92%), cis-PdCl2[P(OPh)3]2 (89%), and cis-PdCl2[PPh2(O-n-Bu)]2 (78%) as catalyst precursors.
- Trzeciak,Bartosz-Bechowski,Ciunik,Niesyty,Ziolkowski
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p. 752 - 759
(2007/10/03)
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- An Exceptionally Simple Biphasic Method for the Metal Catalysed Carbonylation of Chloroarenes
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Bis(tricyclohexylphosphine)palladium dichloride is an active catalyst for the carbonylation of chloroarenes to carboxylic acids.
- Grushin, Vladimir V.,Alper, Howard
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p. 611 - 612
(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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- Photochemical Preparation of the cis Isomers of Dichlorobis(tri-n-alkyl-phosphine)palladium(II) (alkyl = Et, Prn, or Bun); the Crystal-structure Analysis of the Overcrowded n-Propyl Homologue
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Ultraviolet irradiation of the trans forms of the title compounds in nitromethane gives up to 70percent of the labile cis isomers, which can be isolated in crystalline form.Irradiation of a 1:1 mixture of trans- and trans-n3)2Cl2> gives almost entirely a 1:1 mixture of the corresponding cis isomers and only a few percent of cis-n3)Cl2>, indicating a predominantly intramolecular mechanism.Crystals of cis-n3)2Cl2> are monoclinic, with space group P21/m, a=9.729(1), b=13.816(3), c=9.614(1) Angstroem, β=100.77(1) deg, and Z=2.The structure has been refined to R=0.029 for 1 873 reflections collected by a four-circle diffractometer.The cis-planar structure reveals considerable overcrowding .The Pd-P distances are short (mean 2.322 Angstroem) and the Pd-Cl distances long (mean 2.407 Angstroem), attributable to the trans effect.
- Alcock, Nathaniel W.,Kemp, Terence J.,Wimmer, Franz L.
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p. 635 - 638
(2007/10/02)
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