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
收藏
页码：41 / 46
页数：6
相关论文
共 50 条
  • [21] Pd(II)-Catalyzed Enantioselective C-H Activation/C-O Bond Formation: Synthesis of Chiral Benzofuranones
    Cheng, Xiu-Fen
    Li, Yan
    Su, Yi-Ming
    Yin, Feng
    Wang, Jian-Yong
    Sheng, Jie
    Vora, Harit U.
    Wang, Xi-Sheng
    Yu, Jin-Quan
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (04) : 1236 - 1239
  • [22] Pd-catalysed heteroarylations of 3-bromochromen-4-one via C-H bond activation of heteroarenes
    Belkessam, Fatma
    Derridj, Fazia
    Zhao, Liqin
    Elias, Abdelhamid
    Aidene, Mohand
    Djebbar, Saffia
    Doucet, Henri
    TETRAHEDRON LETTERS, 2013, 54 (36) : 4888 - 4891
  • [23] Pd(OAc)2-catalyzed regioselective aromatic C-H bond fluorination
    Lou, Shao-Jie
    Xu, Dan-Qian
    Xia, Ai-Bao
    Wang, Yi-Feng
    Liu, Yun-Kui
    Du, Xiao-Hua
    Xu, Zhen-Yuan
    CHEMICAL COMMUNICATIONS, 2013, 49 (55) : 6218 - 6220
  • [24] C-H Bond Activation Mechanism by a Pd(II)-(μ-O)-Au(0) Structure Unique to Heterogeneous Catalysts
    Takei, Daisuke
    Yatabe, Takafumi
    Yabe, Tomohiro
    Miyazaki, Ray
    Hasegawa, Jun-ya
    Yamaguchi, Kazuya
    JACS AU, 2022, 2 (02): : 394 - 406
  • [25] In site preparation of Pd(II)-MoS2 complex: A new high-efficiency catalyst for alkenylation of heteroaromatics by direct C-H bond activation
    Wang, Sheng
    Deng, Guoqing
    Gu, Jiangjiang
    Hua, Wenwen
    Jia, Xudong
    Xi, Kai
    APPLIED CATALYSIS A-GENERAL, 2015, 508 : 80 - 85
  • [26] Regioselective C-H Bond Activation of Asymmetric Bis(ylide)s Promoted by Pd
    Serrano, Elena
    Soler, Tatiana
    Urriolabeitia, Esteban P.
    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2017, (15) : 2220 - 2230
  • [27] Observing the Agostic Hydrogen in Pd(II)-Catalyzed Aromatic C-H Activation
    Li, Kaiwen
    Jiang, Hongwu
    Zeng, Miao
    Tan, Chen
    Chen, Zhuqi
    Yin, Guochuan
    JOURNAL OF ORGANIC CHEMISTRY, 2022, 87 (24) : 16592 - 16603
  • [28] Stable Pd-nanoparticles catalyzed domino C-H activation/C-N bond formation strategy: An access to phenanthridinones
    Saha, Rajib
    Sekar, Govindasamy
    JOURNAL OF CATALYSIS, 2018, 366 : 176 - 188
  • [29] Factors Affecting the Formation and Transformation of the Intermediates in Pd(II)-Catalyzed Aromatic C-H Activation: A Comprehensive Study with the Pd(II)/LA Platform
    Li, Kaiwen
    Li, Man
    Dong, Shuangfeng
    Li, Shuang-Long
    Chen, Zhuqi
    Liao, Rong-Zhen
    Yin, Guochuan
    JOURNAL OF ORGANIC CHEMISTRY, 2024, 89 (18) : 13540 - 13555
  • [30] Oxygen Activation and Intramolecular C-H Bond Activation by an Amidate-Bridged Diiron(II) Complex
    Jones, Matthew B.
    Hardcastle, Kenneth I.
    Hagen, Karl S.
    MacBeth, Cora E.
    INORGANIC CHEMISTRY, 2011, 50 (14) : 6402 - 6404
12345