FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2326770164> ?p ?o ?g. }

• W2326770164 endingPage "6091" @default.
• W2326770164 startingPage "6077" @default.
• W2326770164 abstract "The reaction of (PiPr3)2NiCl2 with the anthracene adduct (THF)3Mg(η2-C14H10) in THF provides the anthracene adduct (PiPr3)2Ni(η2-C14H10). In aromatic solvents (benzene, toluene, mesitylene) a thermal equilibrium exists between the bis(phosphine)nickel(0) anthracene adduct, (PiPr3)2Ni(η2-C14H10), and the monophosphine solvent adduct, (PiPr3)Ni(η6-solvent). The reaction of (PiPr3)2Ni(η2-C14H10) with 1,2,4,5-C6F4H2 affords the C−H activation product trans-(PiPr3)2NiH(2,3,5,6-C6F4H). The thermodynamic C−F activation product is not obtained even after hours of heating at 100 °C. Similar reactions with 1,2,3,5-C6F4H2 and pentafluorobenzene produce the desired C−H activation products, trans-(PiPr3)2NiH(2,3,4,6-C6F4H) and trans-(PiPr3)2NiH(C6F5), respectively, in >95% yield. The reaction with 1,2,3,4-tetrafluorobenzene did not produce an observable C−H activation product. Unlike previously reported analogous C−H activation products with Ni(PEt3)2 synthons, the bulkier Ni(PiPr3)2 moiety did not provide observable mononuclear or dinuclear η2-fluoroarene adducts. Solutions of Ni(COD)2 with 2 equiv of triisopropylphosphine and 1,2,4,5-C6F4H2 reacted to give the 1,5-cyclooctadiene insertion and rearrangement product, (η3-C8H13)Ni(PiPr3)(2,3,5,6-C6F4H). The same reaction with 1,2,3,5- and 1,2,3,4-C6F4H2 afforded analogous compounds, which demonstrates that C−H bond activation is kinetically accessible at room temperature with 1,2,3,4-tetrafluorobenzene despite the presence of a single ortho-fluorine substituent adjacent to the site of activation. The room-temperature reactions of the C−H activation products (PiPr3)2NiH(ArF) (ArF = 2,3,5,6-C6F4H; C6F5) with 3-hexyne provided a mixture of the alkyne adduct (PiPr3)2Ni(η2-EtC≡CEt), with the liberation of ArFH, and the insertion product (PiPr3)2Ni(CEt═CHEt)(ArF), even in the presence of excess fluorinated aromatic ArFH. The reaction of (PiPr3)2Ni(η2-EtC≡CEt) with 1,2,4,5-C6F4H2 resulted in no reaction at room temperature, but heating at 50 °C provided the insertion product (PiPr3)2Ni(CEt═CHEt)(ArF) as the initial product, followed by the product of reductive elimination, 1,2,4,5-C6F4H-CEt═CHEt. In contrast, the reaction of (PEt3)2Ni(η2-EtC≡CEt) with 1,2,4,5-C6F4H2 at 80 °C slowly produced (PEt3)2Ni(CEt═CHEt)(2,3,5,6-C6F4H), but very little 1,2,4,5-C6F4H-CEt═CHEt." @default.
• W2326770164 created "2016-06-24" @default.
• W2326770164 creator A5042990589 @default.
• W2326770164 creator A5070463408 @default.
• W2326770164 creator A5073400636 @default.
• W2326770164 creator A5075677636 @default.
• W2326770164 date "2010-10-28" @default.
• W2326770164 modified "2023-09-29" @default.
• W2326770164 title "Carbon−Hydrogen Bond Oxidative Addition of Partially Fluorinated Aromatics to a Ni(P^<i>i</i>Pr₃)₂ Synthon: The Influence of Steric Bulk on the Thermodynamics and Kinetics of C−H Bond Activation" @default.
• W2326770164 cites W112766966 @default.
• W2326770164 cites W1485562484 @default.
• W2326770164 cites W1953032341 @default.
• W2326770164 cites W1969635440 @default.
• W2326770164 cites W1969676465 @default.
• W2326770164 cites W1974001124 @default.
• W2326770164 cites W1975096691 @default.
• W2326770164 cites W1975929988 @default.
• W2326770164 cites W1976162057 @default.
• W2326770164 cites W1977960558 @default.
• W2326770164 cites W1978901513 @default.
• W2326770164 cites W1981014742 @default.
• W2326770164 cites W1981224872 @default.
• W2326770164 cites W1982465438 @default.
• W2326770164 cites W1982645967 @default.
• W2326770164 cites W1983134925 @default.
• W2326770164 cites W1983401069 @default.
• W2326770164 cites W1983763827 @default.
• W2326770164 cites W1990236773 @default.
• W2326770164 cites W1995447775 @default.
• W2326770164 cites W1996179594 @default.
• W2326770164 cites W1996532196 @default.
• W2326770164 cites W1998453547 @default.
• W2326770164 cites W1999859373 @default.
• W2326770164 cites W2000420919 @default.
• W2326770164 cites W2000466466 @default.
• W2326770164 cites W2001051532 @default.
• W2326770164 cites W2003810621 @default.
• W2326770164 cites W2006695729 @default.
• W2326770164 cites W2009997608 @default.
• W2326770164 cites W2010189103 @default.
• W2326770164 cites W2011042434 @default.
• W2326770164 cites W2012404887 @default.
• W2326770164 cites W2015981085 @default.
• W2326770164 cites W2016028459 @default.
• W2326770164 cites W2019915647 @default.
• W2326770164 cites W2020149598 @default.
• W2326770164 cites W2025233399 @default.
• W2326770164 cites W2032571285 @default.
• W2326770164 cites W2032873034 @default.
• W2326770164 cites W2033043158 @default.
• W2326770164 cites W2034880948 @default.
• W2326770164 cites W2035823468 @default.
• W2326770164 cites W2040309264 @default.
• W2326770164 cites W2043471890 @default.
• W2326770164 cites W2048977393 @default.
• W2326770164 cites W2049031448 @default.
• W2326770164 cites W2053868123 @default.
• W2326770164 cites W2055927546 @default.
• W2326770164 cites W2059020082 @default.
• W2326770164 cites W2059158057 @default.
• W2326770164 cites W2060835560 @default.
• W2326770164 cites W2062566916 @default.
• W2326770164 cites W2063334178 @default.
• W2326770164 cites W2072053125 @default.
• W2326770164 cites W2074666041 @default.
• W2326770164 cites W2075508712 @default.
• W2326770164 cites W2077871823 @default.
• W2326770164 cites W2078986940 @default.
• W2326770164 cites W2081613332 @default.
• W2326770164 cites W2082561123 @default.
• W2326770164 cites W2083473802 @default.
• W2326770164 cites W2083857215 @default.
• W2326770164 cites W2084301636 @default.
• W2326770164 cites W2087712530 @default.
• W2326770164 cites W2088397466 @default.
• W2326770164 cites W2091702998 @default.
• W2326770164 cites W2107458918 @default.
• W2326770164 cites W2116087305 @default.
• W2326770164 cites W2118398598 @default.
• W2326770164 cites W2121245336 @default.
• W2326770164 cites W2129629428 @default.
• W2326770164 cites W2131919996 @default.
• W2326770164 cites W2141669783 @default.
• W2326770164 cites W2146064363 @default.
• W2326770164 cites W2146390010 @default.
• W2326770164 cites W2150638051 @default.
• W2326770164 cites W2159065552 @default.
• W2326770164 cites W2166173570 @default.
• W2326770164 cites W2170993842 @default.
• W2326770164 cites W2174657615 @default.
• W2326770164 cites W2321693158 @default.
• W2326770164 cites W2331443469 @default.
• W2326770164 cites W2383779760 @default.
• W2326770164 cites W2496564393 @default.
• W2326770164 cites W2940052800 @default.
• W2326770164 cites W2949216143 @default.
• W2326770164 cites W2950440586 @default.
• W2326770164 cites W2953179816 @default.

• next