EPR and DFT Study of Copper(II) Complex with 1,10-Phenanthroline as Catalyst for Oxidation of Cyclohexanol with tert-Butyl Hydroperoxide

被引：2

作者：

Kokorin, A., I ^{[1
,2
]}

Golubeva, E. N. ^{[1
,3
]}

Vinogradov, M. M. ^{[4
]}

Kozlov, Yu N. ^{[1
,2
]}

Shul'pin, G. B. ^{[1
,2
]}

机构：

[1] Russian Acad Sci, NN Semenov Fed Res Ctr Chem Phys, Moscow, Russia

[2] Plekhanov Russian Univ Econ, Moscow, Russia

[3] Moscow MV Lomonosov State Univ, Chem Dept, Moscow, Russia

[4] Russian Acad Sci, Nesmeyanov Inst Organoelement Cpds, Vavilova St, Moscow 119991, Russia

来源：

APPLIED MAGNETIC RESONANCE | 2022年 / 53卷 / 06期

基金：

俄罗斯基础研究基金会;

关键词：

CRYSTAL-STRUCTURES; COMPARATIVE CRYSTALLOGRAPHY; ELECTRONIC-PROPERTIES; STRUCTURAL PATHWAYS; BASIS-SETS; ENERGY; APPROXIMATION; PREDICTION;

D O I：

10.1007/s00723-022-01467-x

中图分类号：

O64 [物理化学（理论化学）、化学物理学]; O56 [分子物理学、原子物理学];

学科分类号：

070203 ; 070304 ; 081704 ; 1406 ;

摘要：

Copper complex with 1,10-phenanthroline was synthesized by a partially modified method. This complex exhibited relatively high catalytic activity in the oxidation of cyclohexanol with tert-butyl hydroperoxide. The complex was characterized by CW EPR spectroscopy (X-band) at room temperature, and results were compared with calculations carried out by the density functional theory (DFT) method. Partial comparison of the EPR and DFT results with X-ray data proves our hypothesis that the structure and spectral properties of the same copper complex in solutions and in a crystalline state may be different.

引用

页码：887 / 894

页数：8

共 35 条

[1]

Altshuler BM., 1972, ELEKTRONNYI PARAMAGN

[2] New Cu4Na4- and Cu5-Based Phenylsilsesquioxanes. Synthesis via Complexation with 1,10-Phenanthroline, Structures and High Catalytic Activity in Alkane Oxidations with Peroxides in Acetonitrile [J].

Astakhov, Grigorii S. ;

Levitsky, Mikhail M. ;

Korlyukov, Alexander A. ;

Shul'pina, Lidia S. ;

Shubina, Elena S. ;

Ikonnikov, Nikolay S. ;

Vologzhanina, Anna V. ;

Bilyachenko, Aleksey N. ;

Dorovatovskii, Pavel, V ;

Kozlov, Yuriy N. ;

Shul'pin, Georgiy B. .

CATALYSTS, 2019, 9 (09)

[3] Quantum calculation of molecular energies and energy gradients in solution by a conductor solvent model [J].

Barone, V ;

Cossi, M .

JOURNAL OF PHYSICAL CHEMISTRY A, 1998, 102 (11) :1995-2001

[4] DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].

BECKE, AD .

PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100

[5] Interaction of DNA with Simple and Mixed Ligand Copper(II) Complexes of 1,10-Phenanthrolines as Studied by DNA-Fiber EPR Spectroscopy [J].

Chikira, Makoto ;

Ng, Chew Hee ;

Palaniandavar, Mallayan .

INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES, 2015, 16 (09) :22754-22780

[6] Coordinated cations in dipicolinato complexes of divalent metal ions [J].

Das, Babulal ;

Baruah, Jubaraj B. .

INORGANICA CHIMICA ACTA, 2010, 363 (07) :1479-1487

[7] Cu(II)-Alkyl Chlorocomplexes: Stable Compounds or Transients? DFT Prediction of their Structure and EPR Parameters [J].

Golubeva, Elena N. ;

Gromov, Oleg I. ;

Zhidomirov, Georgii M. .

JOURNAL OF PHYSICAL CHEMISTRY A, 2011, 115 (28) :8147-8154

[8] Comparison of Density Functional and Correlated Wave Function Methods for the Prediction of Cu(II) Hyperfine Coupling Constants [J].

Gomez-Pineiro, Rogelio J. ;

Pantazis, Dimitrios A. ;

Orio, Maylis .

CHEMPHYSCHEM, 2020, 21 (24) :2667-2679

[9] Optimized Basis Sets for Calculation of Electron Paramagnetic Resonance Hyperfine Coupling Constants: aug-cc-pVTZ-J for the 3d Atoms Sc-Zn [J].

Hedegard, Erik Donovan ;

Kongsted, Jacob ;

Sauer, Stephan P. A. .

JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2011, 7 (12) :4077-4087

[10] A mean-field spin-orbit method applicable to correlated wavefunctions [J].

Hess, BA ;

Marian, CM ;

Wahlgren, U ;

Gropen, O .

CHEMICAL PHYSICS LETTERS, 1996, 251 (5-6) :365-371

← 1 2 3 4 →