Selective Synthesis of Ni(II) and Pd(II) Complexes with either ‘Normal’ or ‘Abnormal’ N‐Heterocyclic Carbene Coordination Modes,ChemistrySelect

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Selective Synthesis of Ni(II) and Pd(II) Complexes with either ‘Normal’ or ‘Abnormal’ N‐Heterocyclic Carbene Coordination Modes
ChemistrySelect ( IF 1.9 ) Pub Date : 2018-03-13 , DOI: 10.1002/slct.201800351
Kel Vin Tan _{1,

2} , Zili Li ₁ , Rebecca E. Karmis ₁ , Peter J. Barnard ₁

Affiliation

A family of Ni(II) and Pd(II) complexes of one bidentate and three tetradentate, N‐heterocyclic carbene (NHC) / amidate ligands have been prepared. The imidazolium salt pro‐ligands used in the synthesis of these complexes were designed to facilitate the ‘abnormal’ NHC coordination mode, through the introduction of either (1) methyl blocking group at the C2 position of the imidazolium units or (2) sterically demanding tert‐butyl imidazolium wingtip substituents or (3) the ligand was macrocyclic in nature. In all cases, the desired complexes were uncharged, with square‐planar coordination geometries about the metal centres. These studies showed that in the case of Ni(II), abnormal NHC complexes could be formed for the C2‐blocked tetradentate ligands only. In contrast for Pd(II), ‘abnormal’ NHC complexes could be prepared from C2‐blocked bidentate and tetradentate ligands with sterically demanding tert‐butyl NHC wingtip substituents. For the macrocyclic tetradentate ligand, Ni(II) and Pd(II) complexes displaying the ‘normal’ NHC coordination mode were obtained.

中文翻译：

具有“正常”或“异常” N-杂环碳原子配位模式的Ni（II）和Pd（II）配合物的选择性合成

制备了一个由一个双齿和三个四齿N-杂环卡宾（NHC）/酰胺基配体组成的Ni（II）和Pd（II）配合物家族。通过在咪唑鎓单元的C2位置引入（1）甲基保护基团或（2）在空间上要求很高的咪唑鎓盐原配体，旨在促进“异常”的NHC配位模式。叔-丁基咪唑鎓翼尖取代基或（3）配体本质上是大环的。在所有情况下，所需的络合物均不带电，金属中心周围的方形平面配位几何形状。这些研究表明，在Ni（II）的情况下，仅C2封闭的四齿配体可能会形成异常的NHC复合物。相比之下，对于Pd（II），“异常” NHC复合物可以由具有空间需求的叔丁基NHC翼尖取代基的C2封闭的双齿和四齿配体制备。对于大环四齿配体，获得了显示“正常” NHC配位模式的Ni（II）和Pd（II）配合物。

更新日期：2018-03-13

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