Generation of nickel(0)-aryne and nickel(II)-biphenyldiyl complexes via in situ dehydrohalogenation of arenes.: Molecular structures of [Ni(2,2′-C6H4C6H4)(dcpe)] and C2-hexabenzotriphenylene
Generation of nickel(0)-aryne and nickel(II)-biphenyldiyl complexes via in situ dehydrohalogenation of arenes.: Molecular structures of [Ni(2,2′-C6H4C6H4)(dcpe)] and C2-hexabenzotriphenylene
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DOI：
10.1016/s0022-328x(02)01667-4
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发表时间：
2003-02-03
影响因子：
2.3
通讯作者：
Willis, AC
中科院分区：
文献类型：
--
作者：
Bennett, MA;Kopp, MR;Willis, AC
芳香族卤化物氯苯、9-溴菲和氯对二甲苯与 2,2,6,6-四甲基哌啶锂 (LiTMP) 在 [Ni(eta(2)-C2H4)(dcpe)] (1) 存在下反应，生成相应的 eta(2)-芳炔配合物 [Ni(eta(2)-aryne)(dcpe)] [aryne = C6H4 (2)， 9,10eta-C14H8 (4) 和 2,3eta-1,4-Me2C6H2 (9)]，它们不能作为纯化合物分离，但根据光谱数据初步鉴定。在 2 的情况下，进一步插入游离苯炔形成联苯二基络合物 [Ni(2,2'-C6H4C6H4)(dcpe)] (3)。除了形成4之外，9,10-菲也在该反应条件下进行环三聚，得到具有C-2对称性的六苯并苯并菲(6)。通过 X 射线衍射分析对化合物 3 和 6 进行了结构表征。 (C) 2002 Elsevier Science B.V. 保留所有权利。
Reactions of the aromatic halides chlorobenzene, 9-bromophenanthrene and chloro-p-xylene with lithium 2,2,6,6-tetramethylpiperidide (LiTMP) in the presence of [Ni(eta(2)-C2H4)(dcpe)] (1) generated the corresponding eta(2)-aryne complexes [Ni(eta(2)-aryne)(dcpe)] [aryne = C6H4 (2), 9,10eta-C14H8 (4) and 2,3eta-1,4-Me2C6H2 (9)], which could not be isolated as pure compounds but were identified tentatively on the basis of spectroscopic data. In the case of 2, further insertion of free benzyne formed the biphenyldiyl complex [Ni(2,2'-C6H4C6H4)(dcpe)] (3). In addition to forming 4, 9,10-phenanthryne also underwent cyclotrimerisation under the reaction conditions to give hexabenzotriphenylene (6), having C-2-symmetry. Compounds 3 and 6 were structurally characterised by X-ray diffraction analyses. (C) 2002 Elsevier Science B.V. All rights reserved.