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- W2050463990 abstract "p-Iodobenzaldehyde is elaborated to the fluorous alcohol p-Rf8(CH2)3C6H4CH(OH)(CH2)2Rf8 (three steps/80%; Rf8 = n-C8F17), which is converted to imine p-Rf8(CH2)3C6H4C(N(CH2)3Rf8)(CH2)2Rf8 (6, two steps/93%) and thioether p-Rf8(CH2)3C6H4CH(S(CH2)3Rf8)(CH2)2Rf8 (12, 64%). Reactions with Pd(OAc)2 (AcOH, 95 °C) give palladacycles with [RC6H3CR′N(R)Pd(μ-OAc)]2 (7, 87%) and [RC6H3CHR′S(R)Pd(μ-OAc)]2 (13, 84%) cores. The former reacts with LiCl and LiI to give the corresponding bridging halide complexes (8, 9); LiCl/PPh3 affords monomeric RC6H3CR′N(R)Pd(Cl)(PPh3) (10). Palladacycles 7–9 and 13 are poorly soluble or insoluble in many solvents at 20–24 °C, but much more soluble at higher temperatures. The CF3C6F11/toluene partition coefficients of 6, 7, 12, and 13 are >91∶<9 (24 °C). Both 7 and 13 are excellent catalyst precursors for Heck reactions of aryl halides. Turnover numbers exceed 106 with phenyl iodide under homogeneous conditions in DMF at 140 °C. The palladacycles precipitate as bridging halides upon cooling, and can in theory be recovered by liquid/solid phase separations. However, since the quantities are small, the solvent C8F17Br is added for recycling. Induction periods in both the first and second cycles, and progressively lower activities, are noted. Transmission electron microscopy indicates the formation of soluble palladium nanoparticles. Together with other data, it is proposed that the nanoparticles are the active catalysts, for which the recyclable palladacycles constitute a steady state source, until exhausted. Complex 7 similarly catalyzes the Suzuki reaction (K3PO4, toluene, 130 °C)." @default.
- W2050463990 created "2016-06-24" @default.
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- W2050463990 date "2002-11-28" @default.
- W2050463990 modified "2023-10-11" @default.
- W2050463990 title "Thermomorphic fluorous imine and thioether palladacycles as precursors for highly active Heck and Suzuki catalysts; evidence for palladium nanoparticle pathways" @default.
- W2050463990 cites W1688618436 @default.
- W2050463990 cites W1963545039 @default.
- W2050463990 cites W1967080231 @default.
- W2050463990 cites W1968589663 @default.
- W2050463990 cites W1972126167 @default.
- W2050463990 cites W1972742713 @default.
- W2050463990 cites W1972758469 @default.
- W2050463990 cites W1977806584 @default.
- W2050463990 cites W1981754097 @default.
- W2050463990 cites W1983390542 @default.
- W2050463990 cites W1986822606 @default.
- W2050463990 cites W1988354257 @default.
- W2050463990 cites W1989558366 @default.
- W2050463990 cites W1990491153 @default.
- W2050463990 cites W2002760371 @default.
- W2050463990 cites W2003110973 @default.
- W2050463990 cites W2005869359 @default.
- W2050463990 cites W2006375884 @default.
- W2050463990 cites W2007487104 @default.
- W2050463990 cites W2008298398 @default.
- W2050463990 cites W2012940736 @default.
- W2050463990 cites W2013172813 @default.
- W2050463990 cites W2015609356 @default.
- W2050463990 cites W2023793464 @default.
- W2050463990 cites W2023895128 @default.
- W2050463990 cites W2024189693 @default.
- W2050463990 cites W2026523439 @default.
- W2050463990 cites W2027227411 @default.
- W2050463990 cites W2028617839 @default.
- W2050463990 cites W2030281756 @default.
- W2050463990 cites W2035224982 @default.
- W2050463990 cites W2037337913 @default.
- W2050463990 cites W2041205483 @default.
- W2050463990 cites W2041250150 @default.
- W2050463990 cites W2042104821 @default.
- W2050463990 cites W2042175392 @default.
- W2050463990 cites W2045369021 @default.
- W2050463990 cites W2045435474 @default.
- W2050463990 cites W2045703603 @default.
- W2050463990 cites W2047974030 @default.
- W2050463990 cites W2052021296 @default.
- W2050463990 cites W2052852142 @default.
- W2050463990 cites W2055118152 @default.
- W2050463990 cites W2056465021 @default.
- W2050463990 cites W2058835752 @default.
- W2050463990 cites W2066151612 @default.
- W2050463990 cites W2068341132 @default.
- W2050463990 cites W2078737036 @default.
- W2050463990 cites W2078865724 @default.
- W2050463990 cites W2080843430 @default.
- W2050463990 cites W2086281945 @default.
- W2050463990 cites W2086659710 @default.
- W2050463990 cites W2089418276 @default.
- W2050463990 cites W2096441356 @default.
- W2050463990 cites W2098482961 @default.
- W2050463990 cites W2101705789 @default.
- W2050463990 cites W2105762154 @default.
- W2050463990 cites W2113584443 @default.
- W2050463990 cites W2130090032 @default.
- W2050463990 cites W2137188824 @default.
- W2050463990 cites W2139838355 @default.
- W2050463990 cites W2146851145 @default.
- W2050463990 cites W2149860506 @default.
- W2050463990 cites W2151222644 @default.
- W2050463990 cites W2162360773 @default.
- W2050463990 cites W2167092049 @default.
- W2050463990 cites W2950042323 @default.
- W2050463990 cites W2950684684 @default.
- W2050463990 cites W2952735401 @default.
- W2050463990 cites W2955669874 @default.
- W2050463990 doi "https://doi.org/10.1039/b208545n" @default.
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