ELECTRONIC TUNING OF ARYLNICKEL(II) COMPLEXES BY PARA SUBSTITUTION OF THE TERDENTATE MONOANIONIC 2,6-BIS[(DIMETHYLAMINO)METHYL]PHENYL LIGAND

被引:127
作者
VANDEKUIL, LA
LUITJES, H
GROVE, DM
ZWIKKER, JW
VANDERLINDEN, JGM
ROELOFSEN, AM
JENNESKENS, LW
DRENTH, W
VANKOTEN, G
机构
[1] UNIV UTRECHT,DEPT MET MEDIATED SYNTH,PADUALAAN 8,3584 CH UTRECHT,NETHERLANDS
[2] UNIV UTRECHT,DEBYE INST,DEPT PHYS INORGAN CHEM,3584 CH UTRECHT,NETHERLANDS
[3] CATHOLIC UNIV NIJMEGEN,DEPT INORGAN CHEM,6525 ED NIJMEGEN,NETHERLANDS
关键词
D O I
10.1021/om00014a020
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Aryl bromides of the type BrC6H2(CH2NMe2)2-2,6-R-4 (R = NH2, MeO, H, Cl, MeC(O)) have been synthesized and have been used to prepare the corresponding organonickel(II) complexes [Ni{C6H2(CH2NMe2)2-2,6-R-4}Br] by an oxidative addition reaction to Ni0(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 C-13 NMR and UV/vis spectroscopy as well as by electrochemistry. The results show that para substitution on the aryl ligand markedly influences the nickel(II) center; electron-donating substituents increase the ease of oxidation to Ni(III), and direct correlations exist between chemical shift data for the carbon atom bonded to nickel and appropriate Hammett parameters.
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收藏
页码:468 / 477
页数:10
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