The coordination chemistry of boron porphyrin complexes B2OX2 (TpYPP) (X = OH, F; Y=Cl, CH3) and their chemical reactivities

被引:9
作者
Cárdenas-Jirón, GI
Espinoza-Leyton, F
Sordo, TL
机构
[1] Univ Santiago Chile, Fac Quim & Biol, Dept Ciencias Quim, Lab Quim Teor, Santiago, Chile
[2] Univ Oviedo, Dept Quim Fis & Analit, E-33006 Oviedo, Spain
关键词
boron; porphyrin; reactivity; Fukui function;
D O I
10.1007/BF02708357
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The structure and coordination chemistry of boron porphyrin complexes B2OX2 (TpYPP) (X = OH, F; Y = Cl, CH3) in connection with its chemical reactivity are analyzed at ab initio density functional theory B3LY-P/6-31G* and restricted Hartree-Fock RHF/6-31G* levels of theory. Global reactivity and local selectivity descriptors are used as adequate tools to analyze the isomerism effect (Z or E isomer) and the substitution effect (X: in axial ligand; or Y: in porphyrin ligand). In all the cases, we find that the E conformation is the most stable one, in agreement with X-ray results, and that a principle of maximum hardness in the isomerism analysis is fullfilled. In the substitution analysis, we find that the three global reactivity indexes (eta, omega, chi) and the two local reactivity indexes (f(k), electrostatic potential) used in this paper predict the same trend when an electron-withdrawing substituent is replaced by an electron donor. Finally, we show that substitution in the porphyrin ligand is slightly more significant than that in the axial ligand.
引用
收藏
页码:515 / 524
页数:10
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