Synthesis, solid-state crystal structure, and reactivity of a monomeric copper(I) anilido complex
Synthesis, solid-state crystal structure, and reactivity of a monomeric copper(I) anilido complex
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DOI：
10.1021/ja0353659
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发表时间：
2003-08-06
影响因子：
15
通讯作者：
White, PS
中科院分区：
文献类型：
--
作者：
Blue, ED;Davis, A;White, PS
通过[（dtbpe）Cu（mu-Cl）]（2）与LiNHPh反应，合成并分离了Cu（I）酰胺配合物（dtbpe）Cu（NHPh）（dtbpe = 1，2-双（二叔丁基膦基）乙烷）。通过红外光谱、多核核磁共振谱和单晶X-射线衍射研究对苯胺配合物进行了表征。固态结构的显著特征包括允许氮基孤对电子与空铜p轨道和苯基取代基的π系统的π相互作用的酰胺基取向。[（dtbpe）Cu（NH 2 Ph）]-[BF 4]的固态X射线衍射研究允许直接比较胺配体转化为酰胺基后的结构特征。（dtbpe）Cu（NHPh）的氨基配体的反应性与亲核性一致。例如，在用[Ph 3C][BF 4]处理时观察到Ph 3CNHPh的形成，并且在室温下与EtX（X = Br或I）反应产生N-乙基苯胺。将（dtbpe）Cu（NHPh）的反应性与八面体和d（6）配合物TpRu（PMe 3）（2）（NHPh）（Tp =三（吡唑基）硼酸盐）的反应性进行比较。
Synthesis and isolation of the Cu(I) amido complex (dtbpe)Cu(NHPh) (dtbpe = 1,2-bis(di-tert-butylphosphino)ethane) is accomplished upon reaction of [(dtbpe)Cu(mu-Cl)](2) with LiNHPh. The anilido complex has been fully characterized by IR spectroscopy and multinuclear NMR spectroscopy as well as by single-crystal X-ray diffraction study. Salient features of the solid-state structure include an amido orientation that allows pi-interaction of the nitrogen-based lone pair with both the empty copper p-orbital and the pi-system of the phenyl substituent. A solid-state X-ray diffraction study of [(dtbpe)Cu(NH2Ph)]-[BF4] has allowed a direct comparison of the structural features upon conversion of the amine ligand to an amido. The reactivity of the amido ligand of (dtbpe)Cu(NHPh) is consistent with nucleophilic character. For example, the formation of Ph3CNHPh is observed upon treatment with [Ph3C][BF4], and reaction at room temperature with EtX (X = Br or I) yields N-ethylaniline. The reactivity of (dtbpe)Cu(NHPh) is compared to that of the octahedral and d(6) complex TpRu(PMe3)(2)(NHPh) (Tp = hydridotris(pyrazolyl)borate).