NHC Nickel Catalyzed Hiyama- and Negishi-Type Cross-Coupling of Aryl Fluorides and Investigations on the Stability of Nickel(II) Fluoroaryl Alkyl Complexes
NHC Nickel Catalyzed Hiyama- and Negishi-Type Cross-Coupling of Aryl Fluorides and Investigations on the Stability of Nickel(II) Fluoroaryl Alkyl Complexes
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NHC 镍催化芳基氟化物的桧山型和根岸型交叉偶联及镍(II)氟芳基烷基配合物的稳定性研究
DOI：
10.1002/ejic.201801477
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发表时间：
2019
影响因子：
2.3
通讯作者：
U. Radius
中科院分区：
文献类型：
--
作者：
M. W. Kuntze-Fechner;C. Kerpen;D. Schmidt;M. Häring;U. Radius
报道了[Ni(IPr2Im)4(µ-COD)]1(iPr2Im=1，3-二异丙基咪唑啉-2-亚甲基，COD=1，4-环辛二烯)在Hiyama-和Negishi-型交叉偶联反应中的反应活性，并合成了几个新的镍氟芳基烷基配合物。1.1当量的平山联轴器。全氟芳烃和1当量。PHSI(OR)_3(R=Me，Et)在5摩尔-%1的催化作用下，以较好的产率得到C-C偶联产物ArF-Ph。在添加剂NMe4F存在下，从PHSI(OR)3向全氟芳烃转移生成ArF-OR和PhSiF(OR)2.C6F6或C7F8(1当量)与二有机锌试剂[ZnR2](R=Me，Et)(2.1当量)在115℃的甲苯溶液中，以5mol-%1为催化剂，只生成微量的ArF-R。然而，核磁共振实验表明，反式[Ni(IPr2Im)2(F)(ArF)]与[ZnR2](R=Me，Et)反应很容易形成镍烷基络合物。在这些研究过程中，以反式[Ni(IPr2Im)2(F)(ArF)](ArF=C6F5，C7F7，C12F9)和[ZnR2](R=Me，Et)(R=Me，Et)(R=Me，Et)为起始原料，合成了一系列新型的镍烷基络合物-[Ni(IPr2Im)2(R)(ARF)](R=Me，C12F94；R=Et；R=Et；R=Et)。反式[Ni(IPr2Im)2(Me)(C6F5)]2在100℃下加热24小时，生成91 %的未反应络合物2，只生成微量的还原消除产物C6F5Me。此外，镍乙基络合物-[Ni(IPr2Im)2(Et)(C6F5)]5也非常稳定，即使在β-氢化物消除方面也是如此。在将该复合体加热到100C 24小时后，仍有26%的 %未反应5。
The reactivity of [Ni(iPr2Im)4(µ‐COD)]1(iPr2Im = 1,3‐diisopropyl‐imidazolin‐2‐ylidene, COD = 1,4‐cyclooctadiene) in Hiyama‐ and Negishi‐type cross‐coupling reactions as well as the synthesis of several novel nickel fluoroaryl alkyl complexes is reported. Hiyama coupling of 1.1 equiv. perfluoroaromatics and 1 equiv. PhSi(OR)3(R = Me, Et) with 5 mol‐% of1as catalyst leads to the C–C coupling product ArF–Ph in good to fair yields. In presence of the additive NMe4F alkoxy transfer from PhSi(OR)3to the perfluoroarene occurs to yield ArF–OR and PhSiF(OR)2. Negishi cross‐coupling between C6F6or C7F8(1 equiv.), diorganozinc reagents [ZnR2] (R = Me, Et) (2.1 equiv.) and 5 mol‐%1as the catalyst in toluene at 115 °C leads to ArF–R only in traces. However, NMR experiments revealed that nickel alkyl complexes are readily formed from the reaction oftrans‐[Ni(iPr2Im)2(F)(ArF)] with [ZnR2] (R = Me, Et). In course of these investigations, a series of novel nickel alkyl complexestrans‐[Ni(iPr2Im)2(R)(ArF)] (R = Me, ArF= C6F52, C7F73, C12F94; R = Et, ArF= C6F55, C7F76, C12F97) have been synthesized in stoichiometric reactions starting fromtrans‐[Ni(iPr2Im)2(F)(ArF)] (ArF= C6F5, C7F7, C12F9) and [ZnR2] (R = Me, Et) in thf at –78 °C. As these nickel alkyl complexes2–7are stable at room temperature in solution for several days with respect to reductive elimination, their thermal stability was investigated. Heatingtrans‐[Ni(iPr2Im)2(Me)(C6F5)]2for 24 hours at 100 °C leads to 91 % unreacted complex2and only traces of reductive elimination product, i.e. C6F5Me, are formed. Furthermore, the nickel ethyl complextrans‐[Ni(iPr2Im)2(Et)(C6F5)]5is also very stable, even with respect to β‐hydride elimination. After heating this complex to 100 °C for 24 hours there is still 26 % unreacted5left.
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影响因子：
2.8
作者：
LaBerge, Nicole A.;Love, Jennifer A.
通讯作者：
Love, Jennifer A.
含氢硅烷的 Si-H 活化产生氢化甲硅烷基和双（甲硅烷基）镍络合物。
影响因子：
4
作者：
T. Zell;T. Schaub;K. Radacki;U. Radius
通讯作者：
U. Radius
影响因子：
2.8
作者：
Baird, Drake A.;Jamal, S.;Johnson, Samuel A.
通讯作者：
Johnson, Samuel A.
DOI：
10.1002/zaac.201100162
发表时间：
2011-10
期刊：
Zeitschrift für anorganische und allgemeine Chemie
影响因子：
--
作者：
T. Zell;U. Radius
通讯作者：
T. Zell;U. Radius
影响因子：
15
作者：
Tian, Ya-Ming;Guo, Xiao-Ning;Marder, Todd B.
通讯作者：
Marder, Todd B.