Structural characterization of copper(I) complexes supported by β-diketiminate ligands with different substitution patterns
Structural characterization of copper(I) complexes supported by β-diketiminate ligands with different substitution patterns
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DOI：
10.1246/bcsj.79.118
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发表时间：
2006-01-15
影响因子：
4
通讯作者：
Itoh, S
中科院分区：
文献类型：
--
作者：
Shimokawa, C;Tachi, Y;Itoh, S
通过使用一系列β-二酮亚胺配体（L-R1，R2（R3-），[（R-3）N-C（R-2）-C（R-1）C（R-2 2）-N（R-3）]（-），参见图1;“β-二酮亚胺”表示烯胺酮亚胺类似物）产生的铜（I）络合物已经通过X射线晶体学分析进行了结构表征。在α-硝基-配体体系中（R-1 = NO2，R-2 = H），所得产物的结构在很大程度上受氮取代基R-3的影响，（β-二酮亚胺基）铜（II）络合物1 [铜（I）的反硝化反应产物]（R-3 = Ph）、头-尾线性配位聚合物铜（I）络合物2（R-3 = Mes，（mesityl））和单核铜（I）络合物3（R-3 = Dipp（2，6-二异丙基苯基））。另一方面，α-氰基-配体（R-1 = CN和R-2 = H或Me）总是得到头-尾配位聚合物铜（I）配合物（4-8），而不管芳香族取代基R-3。在这两个体系中，β-双烯酮亚胺配体表现出U形闭合构象，与铜（I）形成六元螯合环。在α-甲基和α-氢衍生物（R-1 = Me或H，R-2 = H，R-3 = Dipp）的情况下，也获得了具有W形开放构象的β-双烯酮亚胺配体的铜（I）络合物。在这些情况下，得到了双核和四核铜（I）大环配合物9和10。
Copper(I) complexes generated by using a series of beta-diketiminate ligands (L-R1,R2(R3-), [(R-3)N-C(R-2)-C(R-1)C(R-2 2)-N(R-3)](-), see Chart 1; "beta-diketiminate" denotes enaminone imine analogs) have been structurally characterized by X-ray crystallographic analysis. In the alpha-nitro-ligand system (R-1 = NO2 and R-2 = H), the structure of the resulting products were largely affected by the nitrogen substituent R-3, providing bis(beta-diketiminato)copper(II) complex 1 [a product of the disproportionation reaction of copper(I)] (R-3 = Ph), head-to-tail linear coordination polymer copper(I) complex 2 (R-3 = Mes, (mesityl)), and mononuclear copper(I) complex 3 (R-3 = Dipp (2,6-diisopropylphenyl)). On the other hand, alpha-cyano-ligand (R-1 = CN and R-2 = H or Me) always gave head-to-tail coordination polymer copper(I) complexes (4-8) regardless of the aromatic substituent R-3. In both systems, beta-diketiminate ligands exhibited a U-shaped closed conformation, forming a six-membered chelate ring with copper(I). Copper(I) complexes with a beta-diketiminate ligand with a W-shaped open conformation were also obtained in the case of alpha-methyl and alpha-hydrogen derivatives (R-1 = Me or H, R-2 = H, and R-3 = Dipp). In these cases, the dinuclear and tetranuclear copper(l) macrocyclic complexes 9 and 10 were obtained.