[(NHC)Cu(I)-ER3] Complexes (ER3 = SiMe2Ph, SiPh3, SnMe3): From Linear, Mononuclear Complexes to Polynuclear Complexes with Ultrashort Cu(I)···Cu(I) Distances.
[(NHC)Cu(I)-ER3] Complexes (ER3 = SiMe2Ph, SiPh3, SnMe3): From Linear, Mononuclear Complexes to Polynuclear Complexes with Ultrashort Cu(I)···Cu(I) Distances.
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DOI：
10.1021/acs.inorgchem.6b00210
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发表时间：
2016-05
影响因子：
4.6
通讯作者：
Jacqueline Plotzitzka;C. Kleeberg
中科院分区：
文献类型：
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作者：
Jacqueline Plotzitzka;C. Kleeberg
通过相应的 [(NHC)Cu-OtBu] 络合物与各自的反应，以良好的产率合成了一系列 [(NHC)Cu-ER3] 类型的络合物（NHC = IDipp、IMes、ItBu、Me2IMe 和 ER3 = SiMe2Ph、SiPh3、SnMe3）和 [(NHC)Cu-R']（NHC = IDipp、Me2IMe 和 R' = Ph、C=CPh）。甲硅烷基硼烷 pinB-ER3 (pin = OCMe2CMe2O; ER3 = SiMe2Ph, SiPh3)、甲锡烷基硼烷 ((C2H4)(iPrN)2)B-SnMe3 或硼酸酯 pinB-R' (R' = Ph, C≡CPh)。通过X射线衍射分析系统地研究了所有配合物的固体结构。配合物 [(NHC)Cu-ER3] 的固态结构显示出结构基序对 NHC 配体空间特性的依赖性。空间要求较高的 NHC 配体（IDipp、IMes、ItBu）会产生单体、线性配合物 [(NHC)Cu-ER3]，而对于要求较低的 Me2IMe 配体，则观察到具有超短 Cu·Cu 距离的多核、μ-ER3 桥配合物。对于相关配合物[(NHC)Cu-R']，没有实现具有桥接阴离子配体的类似配合物。相反，无论 NHC 配体如何，都会形成不同类型的线性配位铜配合物。 (29)Si 异核溶液 NMR 光谱数据显示（固态）单体和二聚复合物的化学位移明显不同，表明溶液中也有不同的结构类型。这与固态和溶液中三核配合物 [(Me2IMe)Cu-SnMe3]3 的观察结果非常吻合。初步催化研究表明，除了已建立的 [(IDipp)Cu-OtBu] 配合物之外，[(NHC)Cu-OtBu] 配合物 (NHC = ItBu, Me2IMe) 也是用 pinB-SiMe2Ph 进行醛和 α,β-不饱和酮硅烷化的有效预催化剂。
A series of complexes of the type [(NHC)Cu-ER3] (NHC = IDipp, IMes, ItBu, Me2IMe, and ER3 = SiMe2Ph, SiPh3, SnMe3) and [(NHC)Cu-R'] (NHC = IDipp, Me2IMe and R' = Ph, C≡CPh) was synthesized in good yields by the reaction of the corresponding [(NHC)Cu-OtBu] complex with the respective silylborane pinB-ER3 (pin = OCMe2CMe2O; ER3 = SiMe2Ph, SiPh3), the stannylborane ((C2H4)(iPrN)2)B-SnMe3, or a boronic acid ester pinB-R' (R' = Ph, C≡CPh). Solid structures of all complexes were systematically studied by X-ray diffraction analysis. The solid state structures of the complexes [(NHC)Cu-ER3] show a dependence of the structural motif from the steric properties of the NHC ligand. The sterically demanding NHC ligands (IDipp, IMes, ItBu) lead to monomeric, linear complexes [(NHC)Cu-ER3], while with the less demanding Me2IMe ligand, polynuclear, μ-ER3-bridged complexes with ultrashort Cu···Cu distances are observed. For the related complexes [(NHC)Cu-R'] no analogous complexes with bridging anionic ligands are realized. Instead, irrespective of the NHC ligand, linear coordinated copper complexes of different types are formed. (29)Si heteronuclear solution NMR spectroscopic data on [(NHC)Cu(I)-SiR3] exhibit distinctly different chemical shifts for the (in the solid state) monomeric and dimeric complexes suggesting different structure types also in solution. This agrees well with the observation of a trinuclear complex [(Me2IMe)Cu-SnMe3]3 both in the solid state and in solution. Initial catalytic studies suggest that [(NHC)Cu-OtBu] complexes (NHC = ItBu, Me2IMe) are, in addition to the established [(IDipp)Cu-OtBu] complex, efficient precatalysts for the silylation of aldehydes and α,β-unsaturated ketones with pinB-SiMe2Ph.