C-H Activation of Terminal Alkynes by Tris-(3,5-dimethylpyrazolyl)boraterhodiumneopentylisocyanide: New Metal-Carbon Bond Strengths

被引：20

作者：

Choi, Gyeongshin ^{[2
]}

Morris, James ^{[1
]}

Brennessel, William W. ^{[1
]}

Jones, William D. ^{[1
]}

机构：

[1] Univ Rochester, Dept Chem, Rochester, NY 14627 USA

[2] Osaka Univ, Grad Sch Engn Sci, Dept Chem, Toyonaka, Osaka 5608531, Japan

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2012年 / 134卷 / 22期

关键词：

POTENTIAL BASIS-SETS; POLARIZATION FUNCTIONS; REDUCTIVE ELIMINATION; COMPLEXES; THERMOCHEMISTRY; FUNCTIONALIZATION; SENSITIVITY; OLEFINATION; PHOTOLYSIS; MECHANISM;

D O I：

10.1021/ja301095r

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

C-H bond activation of terminal alkynes by [Tp'Rh(CNneopentyl)] (Tp' = hydridotris - (3,5-dimethylpyrazolyl)borate) resulted in the formation of terminal C-H bond activation products Tp'Rh(CNneopentyl)(C CR)H (R = t-Bu, SiMe3, hexyl, CF3, p-MeOC6H4, Ph, and p-CF3C6H4). A combination of kinetic selectivity determined in competition reactions and activation energy for reductive elimination has allowed for the calculation of relative Rh-C-alkynyl bond strengths. The bond strengths of Rh-C-alkynyl products are noticeably higher than those of Rh-C-aryl and RE-C-alkyl analogues. The relationship between M-C and C-H bond strengths showed a linear correlation (slope RM-C/H-C = 1.32), and follows energy correlations previously established for unsubstituted sp(2) and sp(3) C-H bonds in aliphatic and aromatic hydrocarbons.

引用

页码：9276 / 9284

页数：9

共 45 条

[1] SYNTHESIS AND STRUCTURE OF TRANS-[MCL(=C=CHR)(PIPR3)2] (M=RH,IR) - THE 1ST SQUARE-PLANAR VINYLIDENEMETAL COMPLEXES [J].

ALONSO, FJG ;

HOHN, A ;

WOLF, J ;

OTTO, H ;

WERNER, H .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1985, 24 (05) :406-408

[2] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

[3] Selective ortho C-H activation of haloarenes by an Ir(I) system [J].

Ben-Ari, E ;

Gandelman, M ;

Rozenberg, H ;

Shimon, LJW ;

Milstein, D .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (16) :4714-4715

[4] Selectivities in hydrocarbon activation: Kinetic and thermodynamic investigations of reversible 1,2-RH-elimination from (silox)(2)((Bu3SiNH)-Bu-t)TiR (silox = (Bu3SiO)-Bu-t) [J].

Bennett, JL ;

Wolczanski, PT .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (44) :10696-10719

[5] Selective Pd-catalyzed oxidative coupling of anilides with olefins through C-H bond activation at room temperature [J].

Boele, MDK ;

van Strijdonck, GPF ;

de Vries, AHM ;

Kamer, PCJ ;

de Vries, JG ;

van Leeuwen, PWNM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (08) :1586-1587

[6] ORGANOMETALLIC CHEMISTRY OF VINYLIDENE AND RELATED UNSATURATED CARBENES [J].

BRUCE, MI .

CHEMICAL REVIEWS, 1991, 91 (02) :197-257

[7] Indirect ortho functionalization of substituted toluenes through ortho olefination of N,N-dimethylbenzylamines tuned by the acidity of reaction conditions [J].

Cai, Guixin ;

Fu, Ye ;

Li, Yizhou ;

Wan, Xiaobing ;

Shi, Zhangjie .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (24) :7666-7673

[8] Acylation of five-membered N-heteroaromatic compounds by ruthenium carbonyl-catalyzed direct carbonylation at a C-H bond [J].

Chatani, N ;

Fukuyama, T ;

Tatamidani, H ;

Kakiuchi, F ;

Murai, S .

JOURNAL OF ORGANIC CHEMISTRY, 2000, 65 (13) :4039-4047

[9] Bond energy M-C/H-C correlations:: dual theoretical and experimental approach to the sensitivity of M-C bond strength to substituents [J].

Clot, E ;

Besora, M ;

Maseras, F ;

Mégret, C ;

Eisenstein, O ;

Oelckers, B ;

Perutz, RN .

CHEMICAL COMMUNICATIONS, 2003, (04) :490-491

[10] Validation of the M-C/H-C bond enthalpy relationship through application of density functional theory [J].

Clot, Eric ;

Megret, Claire ;

Eisenstein, Odile ;

Perutz, Robin N. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (25) :8350-8357

← 1 2 3 4 5 →