Electronic Tuning of Arylnickel(II) Complexes by Para Substitution of the Terdentate Monoanionic 2,6-Bis[(dimethylamino)methyl]phenyl Ligand
Electronic Tuning of Arylnickel(II) Complexes by Para Substitution of the Terdentate Monoanionic 2,6-Bis[(dimethylamino)methyl]phenyl Ligand
复制标题
通过对位取代三齿单阴离子 2,6-双[(二甲氨基)甲基]苯基配体对芳基镍 (II) 配合物进行电子调谐
DOI：
10.1021/om00014a020
复制
发表时间：
1994
期刊：
影响因子：
2.8
通讯作者：
W. Drenth
中科院分区：
文献类型：
--
作者：
G. Koten;L. A. V. D. Kuil;J. Luitjes;D. M. Grove;J. W. Zwikker;J. Linden;A. Roelofsen;L. Jenneskens;W. Drenth
合成了BrCeHZ(CHzNMez)z-2，6-R-4(R=NHz，MeO，H，C1，MEC(0))芳基溴化物，并与NiO(COD)2(COD=环辛烷-1，5-二烯)进行氧化加成反应，合成了相应的有机镍(I)配合物[NitCsHZ(CHzNMez)z-2，6-R-4]BrL。用~(13)C核磁共振、UV/Vis光谱和电化学方法研究了N，C，N‘-三齿-芳基配体的对位取代基对镍配合物电子性质的影响。结果表明，芳基上的对位取代对镍(I1)中心有显著影响，给电子取代基易氧化成NiIII，镍上碳原子的化学位移数据与合适的Hammett参数之间存在着直接的相关性。
Aryl bromides of the type BrCeHz(CHzNMez)z-2,6-R-4 (R = NHz, MeO, H, C1, MeC(0)) have been synthesized and have been used to prepare the corresponding organonickel(I1) complexes [NitCsHz(CHzNMez)z-2,6-R-4)Brl by an oxidative addition reaction to Nio(COD)2 (COD = cycloocta-1,5-diene). The effect that the para substituent of the monoanionic, N,C,N' terdentate, aryl ligand has on the electronic properties of the nickel complexes has been investigated by 13C NMR and UV/vis spectroscopy as well as by electrochemistry. The results show that para substitution on the aryl ligand markedly influences the nickel(I1) center; electron-donating substituents increase the ease of oxidation to NiIII, and direct correlations exist between chemical shift data for the carbon atom bonded to nickel and appropriate Hammett parameters.