Synthesis and Reactivity of Two-Coordinate Ni(I) Alkyl and Aryl Complexes
Synthesis and Reactivity of Two-Coordinate Ni(I) Alkyl and Aryl Complexes
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DOI：
10.1021/ja4095236
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发表时间：
2013-12-11
影响因子：
15
通讯作者：
Hillhouse, Gregory L.
中科院分区：
文献类型：
--
作者：
Laskowski, Carl A.;Bungum, Donald J.;Hillhouse, Gregory L.
[（IPr）Ni（μ-Cl）]（2）（1-Cl; IPr = 1，3-双（2，6-二异丙基苯基）咪唑啉-2-亚基）与ClMg{CH（SiMe 3）（2）}中心点Et 2 O反应，得到一个双配位Ni（I）烷基配合物（IPr）Ni{CH（SiMe 3）（2）}（2）。类似的二配位芳基衍生物（IPr）Ni（dmp）（dmp = 2，6-二均三甲苯基苯基）可以类似地由Li（dmp）和1-Cl制备。2与烷基溴反应得到三配位的卤化镍配合物（IPr）Ni{CH（SiMe 3）（2）}Br。自由基机制的证据来解释2与卤代烷的反应。
Reaction of [(IPr)Ni(mu-Cl)](2) (1-Cl; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) with ClMg{CH(SiMe3)(2)}center dot Et2O affords (IPr)Ni{CH(SiMe3)(2)} (2), a two-coordinate Ni(I) alkyl complex. An analogous two-coordinate aryl derivative, (IPr)Ni(dmp) (dmp = 2,6-dimesitylphenyl), can be similarly prepared from Li(dmp) and 1-Cl. Reaction of 2 with alkyl bromides gives the three-coordinate Ni(II) alkyl halide complex (IPr)Ni{CH(SiMe3)(2)}Br. Evidence for a radical mechanism is presented to explain the reaction of 2 with alkyl halides.