Is the polarization of the C=C bond imperative for bifunctional outer-sphere C=C hydrogenation?

被引：5

作者：

Ai, Xinliang ^{[1
]}

Xie, Xiaofeng ^{[1
]}

Song, Xueqing ^{[1
]}

Li, Longfei ^{[1
]}

Schaefer III, Henry F. ^{[2
]}

机构：

[1] Hebei Univ, Coll Pharm, Key Lab Pharmaceut Qual Control Hebei Prov, Key Lab Med Chem & Mol Diagnosis,Minist Educ, Baoding 071002, Hebei, Peoples R China

[2] Univ Georgia, Ctr Computat Quantum Chem, Athens, GA 30602 USA

来源：

ORGANIC CHEMISTRY FRONTIERS | 2023年 / 10卷 / 05期

基金：

中国国家自然科学基金;

关键词：

CATALYTIC-HYDROGENATION; ENANTIOSELECTIVE HYDROGENATION; HOMOGENEOUS HYDROGENATION; SPLIT-VALENCE; BASIS-SETS; DESIGN; COMPLEXES; ALKENES; MILD;

D O I：

10.1039/d2qo02020c

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Understanding controlling factors is important for the development of bifunctional outer-sphere CC hydrogenations. A dominant view is that the polarization of CC bonds is imperative for these reactions. However, the present comparative DFT study suggests that the polarization of CC bonds is not the controlling factor. Instead, the "push-pull " type pi-conjugative effect can decrease activation barriers and contribute to outer-sphere bifunctional CC bond hydrogenations. What is more, this study shows the feasibility of the asymmetric bifunctional outer-sphere CC hydrogenation.

引用

页码：1301 / 1308

页数：8

共 58 条

[1] Hexene hydrogenation catalysed by the complex monohydrid complexes: A DFT study of associated vs dissociated pathways [J].

Achour, Sofiene ;

Hosni, Zied ;

Tangour, Bahoueddine .

JOURNAL OF MOLECULAR GRAPHICS & MODELLING, 2020, 98

[2] "Push-Pull π plus /π-" (PPππ) Systems in Catalysis [J].

Alegre-Requena, Juan V. ;

Marques-Lopez, Eugenia ;

Herrera, Raquel P. .

ACS CATALYSIS, 2017, 7 (10) :6430-6439

[3] First-Row Transition Metal (De)Hydrogenation Catalysis Based On Functional Pincer Ligands [J].

Alig, Lukas ;

Fritz, Maximilian ;

Schneider, Sven .

CHEMICAL REVIEWS, 2019, 119 (04) :2681-2751

[4] Contribution of DFT to the optimization of Ni-based catalysts for dry reforming of methane: a review [J].

Alioui, Oualid ;

Badawi, Michael ;

Erto, Alessandro ;

Amin, Mohammed A. ;

Tirth, Vineet ;

Jeon, Byong-Hun ;

Islam, Saiful ;

Balsamo, Marco ;

Virginie, Mirella ;

Ernst, Barbara ;

Benguerba, Yacine .

CATALYSIS REVIEWS-SCIENCE AND ENGINEERING, 2023, 65 (04) :1468-1520

[5] Cobalt-Catalyzed Hydrogenation Reactions Enabled by Ligand-Based Storage of Dihydrogen [J].

Anferov, Sophie W. ;

Filatov, Alexander S. ;

Anderson, John S. .

ACS CATALYSIS, 2022, 12 (16) :9933-9943

[6] Push-pull architecture eliminates chain length effects on exciton dissociation [J].

Aplan, Melissa P. ;

Lee, Youngmin ;

Wilkie, Carly A. ;

Wang, Qing ;

Gomez, Enrique D. .

JOURNAL OF MATERIALS CHEMISTRY A, 2018, 6 (45) :22758-22767

[7] A highly contorted push-pull naphthalenediimide dimer and evidence of intramolecular singlet exciton fission [J].

Bansal, Deepak ;

Kundu, Arup ;

Singh, Vijay Pal ;

Pal, Arun K. ;

Datta, Ayan ;

Dasgupta, Jyotishman ;

Mukhopadhyay, Pritam .

CHEMICAL SCIENCE, 2022, 13 (39) :11506-11512

[8] A new insight into the push-pull effect of substituents via the stilbene-like model compounds [J].

Cao, Chaotun ;

Zeng, Zhao ;

Cao, Chenzhong .

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 2022, 35 (04)

[9] Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections [J].

Chai, Jeng-Da ;

Head-Gordon, Martin .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2008, 10 (44) :6615-6620

[10] OLEFIN CO-ORDINATION COMPOUNDS .3. INFRA-RED SPECTRA AND STRUCTURE - ATTEMPTED PREPARATION OF ACETYLENE COMPLEXES [J].

CHATT, J ;

DUNCANSON, LA .

JOURNAL OF THE CHEMICAL SOCIETY, 1953, (OCT) :2939-2947

← 1 2 3 4 5 6 →