Experimental and theoretical examination of C-CN and C-H bond activations of acetonitrile using zerovalent nickel

被引：0

作者：

Ateşin, Tülay A. ^{[1
]}

Li, Ting ^{[1
]}

Lachaize, Sébastien ^{[1
]}

Brennessel, William W. ^{[1
]}

García, Juventino J. ^{[2
]}

Jones, William D. ^{[1
]}

机构：

[1] Department of Chemistry, University of Rochester, Rochester, NY 14627, United States

[2] Facultad de Química, Universidad Nacional Autónoma de México, México, D.F. 04510, Mexico

来源：

| 1600年 / American Chemical Society, 2540 Olentangy River Road, P.O. Box 3337, Columbus, OH 43210-3337, United States卷 / 129期

关键词：

Experimental and density functional theory show that the reaction of acetonitrile with a zerovalent nickel bis(dialkylphosphino)ethane fragment (alkyl = methyl; isopropyl) proceeds via initial exothermic formation of an η2-nitrile complex. Three well-defined transition states have been found on the potential energy surface between the η2-nitrile complex and the activation products. The lowest energy transition state is an η3-acetonitrile complex; which connects the η2- nitrile to a higher energy η3-acetonitrile intermediate with an agostic C-H bond; while the other two lead to cleavage of either the C-H or the C-CN bonds. Gas-phase calculations show C-CN bond activation to be endothermic; which contradicts the observation of thermal C-CN activation in THF. Therefore; the effect of solvent was taken into consideration by using the polarizable continuum model (PCM); whereupon the activation of the C-CN bond was found to be exothermic. Furthermore the C-CN bond activation was found to be favored exclusively over C-H bond activation due to the strong thermodynamic driving force and slightly lower kinetic barrier. © 2007 American Chemical Society;

D O I：

暂无

中图分类号：

学科分类号：

摘要：

Journal article (JA)

引用

共 50 条

[1] Experimental and theoretical examination of C-CN and C-H bond activations of acetonitrile using zerovalent nickel
Atesin, Tulay A.
Li, Ting
Lachaize, Sebastien
Brennessel, William W.
Garcia, Juventino J.
Jones, William D.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (24) : 7562 - 7569
[2] Experimental and theoretical examination of C-CN bond activation of benzonitrile using zerovalent nickel
Atesin, Tuelay A.
Li, Ting
Lachaize, Sebastien
Garcia, Juventino J.
Jones, William D.
ORGANOMETALLICS, 2008, 27 (15) : 3811 - 3817
[3] Experimental and theoretical examination of C-CN bond activation of aromatic nitrites using zerovalent nickel
Li, Ting
Jones, William D.
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2009, 238
[4] INOR 809-Experimental and theoretical examination of C-CN bond activation of arylnitrile using zerovalent nickel
Li, Ting
Atesin, Tulay A.
Lachaize, Sebastien
Garcia, Juventino J.
Jones, William D.
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2008, 235
[5] C-H and C-CN bond activation of acetonitrile with [Cp*Rh(PMe3)]: An experimental and theoretical investigation
Evans, Meagan E.
Li, Ting
Jones, William D.
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2010, 240
[6] Copper-Catalyzed Aromatic C-H Bond Cyanation by C-CN Bond Cleavage of Inert Acetonitrile
Kou, Xuezhen
Zhao, Mengdi
Qiao, Xixue
Zhu, Yamin
Tong, Xiaofeng
Shen, Zengming
CHEMISTRY-A EUROPEAN JOURNAL, 2013, 19 (50) : 16880 - 16886
[7] C-H and C-CN Bond Activation of Acetonitrile and Succinonitrile by [Tp′Rh(PR3)]
Tanabe, Taro
Evans, Meagan E.
Brennessel, William W.
Jones, William D.
ORGANOMETALLICS, 2011, 30 (04) : 834 - 843
[8] Advances in C-CN Bond Formation via C-H Bond Activation
Ping, Yuanyuan
Ding, Qiuping
Peng, Yiyuan
ACS CATALYSIS, 2016, 6 (09): : 5989 - 6005
[9] C-CN Bond Activation of Acetonitrile using Cobalt(I)
Xu, Hongwei
Williard, Paul G.
Bernskoetter, Wesley H.
ORGANOMETALLICS, 2012, 31 (05) : 1588 - 1590
[10] Controlling the Selectivity for C-H and C-CN Bond Activation at Rhodium: A DFT Examination of Ligand Effects
Evans, Meagan E.
Jones, William D.
ORGANOMETALLICS, 2011, 30 (12) : 3371 - 3377

← 1 2 3 4 5 →