Carbon−Hydrogen Bond Oxidative Addition of Partially Fluorinated Aromatics to a Ni(P<sup><i>i</i></sup>Pr<sub>3</sub>)<sub>2</sub>Synthon: The Influence of Steric Bulk on the Thermodynamics and Kinetics of C−H Bond Activation
作者:Jillian A. Hatnean、Robert Beck、Jenna D. Borrelli、Samuel A. Johnson
DOI:10.1021/om1008499
日期:2010.11.22
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
(P的反应我镨3)2的NiCl 2与蒽加合物(THF)3的Mg(η 2 -C 14 ħ 10)在THF提供的蒽加合物(P我镨3)2的Ni(η 2 -C 14 H 10)。在芳族溶剂(苯,甲苯,均三甲苯)双之间存在热平衡(膦)镍(0)蒽加成物,(P我镨3)2的Ni(η 2 -C 14 ħ 10),以及单膦溶剂加成物,(P我镨3)的Ni(η 6 -溶剂)。的(P反应我镨3)2的Ni(η 2 -C 14 ħ 10)与1,2,4,5--C 6 ˚F 4 ħ 2次,得到C-H活化产物的反式(P -我镨3)2 NiH(2,3,5,6-C 6 F 4 H)。即使在100°C下加热数小时,也无法获得热力学C-F活化产物。与1,2,3,5-C 6 F 4 H的相似反应2和五氟苯产生所需的CH活化产物,反式-(P i Pr 3)2 NiH(2,3,4,6-C 6 F 4 H)和反式-(P i Pr 3)2 NiH(C