A DFT study on the difference of C-H bond activation by Pd(II) and Pd(IV) complex

被引：4

作者：

Zhao, Xue ^{[1
]}

Sun, Chuanzhi ^{[1
]}

Lu, Yating ^{[1
]}

Xing, Zhong ^{[1
]}

Sun, Nan ^{[1
]}

Chen, Dezhan ^{[1
]}

机构：

[1] Shandong Normal Univ, Collaborat Innovat Ctr Functionalized Probes Chem, Shandong Prov Key Lab Clean Prod Fine Chem, Key Lab Mol & Nano Probes,Minist Educ,Coll Chem C, Jinan 250014, Peoples R China

来源：

COMPUTATIONAL AND THEORETICAL CHEMISTRY | 2015年 / 1056卷

关键词：

Density functional theory; C-H activation; Pd(II) and Pd(IV) complex; Site selectivity; REDUCTIVE ELIMINATION; ARYLATION; REACTIVITY; MECHANISM; FUNCTIONALIZATION; REAGENTS; FLUORINATION; OXIDATION; ELECTRON; LIGANDS;

D O I：

10.1016/j.comptc.2015.01.003

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The reaction mechanism of Pd(II) and Pd(IV) complex catalyzed C-H bond activation was investigated by density functional theory. The difference between the two complex catalyzed reactions was uncovered. It can be concluded from the calculated results that the energy barrier difference (E-Ab-E-Aa) of Pd(II) complex catalyzed reaction is higher than that (E-Bb-E-Ba) of Pd(IV) complex catalyzed reaction in the rate-determining step, which induces the higher site selectivity of Pd(II) complex catalyzed reaction. The degree of energy barrier difference should be related to synergic effect between the steric effect of methyl and the space distribution of HOMO-C-p and LUMO-Pd-d orbitals. In other words, this synergic effect should be responsible for the different site selectivity between Pd(II) and Pd(IV) complex catalyzed C-H bond activation. (C) 2015 Elsevier B.V. All rights reserved.

引用

页码：41 / 46

页数：6

共 50 条

[41] Direct arylation of cyclic enamides via Pd(II)-catalyzed C-H activation
Zhou, Hai
Chung, Wan-Jun
Xu, Yun-He
Loh, Teck-Peng
CHEMICAL COMMUNICATIONS, 2009, (23) : 3472 - 3474
[42] DFT Study on the Mechanism of Tandem Oxidative Acetoxylation/Ortho C-H Activation/Carbocyclization Catalyzed by Pd(OAc)2
Li, Hui
Ma, Xuelu
Zhang, Baohua
Lei, Ming
ORGANOMETALLICS, 2016, 35 (19) : 3301 - 3310
[43] C–C bond activation enabled by dyotropic rearrangement of Pd(iv) species
Jian Cao
Hua Wu
Qian Wang
Jieping Zhu
Nature Chemistry, 2021, 13 : 671 - 676
[44] Amine directed Pd(II)-catalyzed C-H bond functionalization under ambient conditions
Haffemayer, Benjamin
Gulias, Moises
Gaunt, Matthew J.
CHEMICAL SCIENCE, 2011, 2 (02) : 312 - 315
[45] Dehydrogenative and decarboxylative C-H alkynylation of heteroarenes catalyzed by Pd(II)-carbene complex
Parsharamulu, Thupakula
Reddy, Police Vishnuvardhan
Likhar, Pravin R.
Kantarn, Mannepalli Lakshmi
TETRAHEDRON, 2015, 71 (13) : 1975 - 1981
[46] C-H bond activation in the formation of an osmium(IV) metallacycle
Koch, JL
Shapley, PA
ORGANOMETALLICS, 1999, 18 (05) : 814 - 816
[47] C-H bond activation of hydrocarbons by an imidozirconocene complex
Hoyt, HM
Michael, FE
Bergman, RG
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (04) : 1018 - 1019
[48] Highly Selective Activation of C-H Bond and Inhibition of C-C Bond Cleavage by Tuning Strong Oxidative Pd Sites
Guo, Meng
Ma, Peijie
Wei, Lu
Wang, Jiayi
Wang, Zhiwei
Zheng, Kun
Cheng, Daojian
Liu, Yuxi
Dai, Hongxing
Guo, Guangsheng
Duan, Erhong
Deng, Jiguang
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2023, 145 (20) : 11110 - 11120
[49] Triazole-Auxillary Pd catalyzed C-H activation
Ye, Xiaohan
Shi, Xiaodong
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2012, 244
[50] β-C-H bond functionalization of ketones and esters by cationic Pd complexes
Li, Yi-Hao
Chekshin, Nikita
Lu, Yilin
Yu, Jin-Quan
NATURE, 2025, 637 (8046) : 608 - 614

← 1 2 3 4 5 →