Silyl Ligand Mediated Reversible β-Hydrogen Elimination and Hydrometalation at Palladium

被引：26

作者：

Takaya, Jun ^{[1
]}

Iwasawa, Nobuharu ^{[1
]}

机构：

[1] Tokyo Inst Technol, Dept Chem, Meguro Ku, Tokyo 1528551, Japan

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2014年 / 20卷 / 37期

关键词：

hydride ligands; ligand effects; palladium; reaction mechanisms; silicon; TERTIARY PHOSPHINE-LIGANDS; PINCER COMPLEXES; BOND ACTIVATION; SI-H; THERMAL-DECOMPOSITION; CATALYTIC BEHAVIOR; METAL-COMPLEXES; CARBON-DIOXIDE; PSIP; BEARING;

D O I：

10.1002/chem.201403220

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The mechanism and origin of the facile beta-hydrogen elimination and hydrometalation of a palladium complex bearing a phenylene-bridged PSiP pincer ligand are clarified. Experimental and theoretical studies demonstrate a new mechanism for beta-hydrogen elimination and hydrometalation mediated by a silyl ligand at palladium, which enables direct interconversion between an ethylpalladium(II) complex and an eta(2)-(Si-H)palladium(0) complex without formation of a square-planar palladium(II) hydride intermediate. The flexibility of the PSiP pincer ligand enables it to act as an efficient scaffold to deliver the hydrogen atom as a hydride ligand.

引用

页码：11812 / 11819

页数：8

共 51 条

[1]

[Anonymous], ANGEW CHEM

[2] Hydrosilylation vs. [2+2]-cycloaddition:: A theoretical study with iron and ruthenium complexes [J].

Boehme, Uwe .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2006, 691 (21) :4400-4410

[3] Dynamic processes in silyl palladium complexes:: Evidence for intermediate Si-H and Si-Si σ-complexes [J].

Boyle, Robert C. ;

Pool, Douglas ;

Jacobsen, Heiko ;

Fink, Mark J. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (28) :9054-9055

[4] Ligand-Controlled Remarkable Regio- and Stereodivergence in Intermolecular Hydrosilylation of Internal Alkynes: Experimental and Theoretical Studies [J].

Ding, Shengtao ;

Song, Li-Juan ;

Chung, Lung Wa ;

Zhang, Xinhao ;

Sun, Jianwei ;

Wu, Yun-Dong .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (37) :13835-13842

[5] Insights into the Heck reaction with PCP pincer palladium(II) complexes [J].

Eberhard, MR .

ORGANIC LETTERS, 2004, 6 (13) :2125-2128

[6]

Espinet P, 2003, CURR METH INORG CHEM, V3, P293

[7] Retardation of β-hydrogen elimination in PNP Pincer complexes of Pd [J].

Fafard, Claudia M. ;

Ozerov, Oleg V. .

INORGANICA CHIMICA ACTA, 2007, 360 (01) :286-292

[8] Synthesis, Structure, and Reactivity of Hydridoiridium Complexes Bearing a Pincer-Type PSiP Ligand [J].

Fang, Hongyun ;

Choe, Yoong-Kee ;

Li, Yonghua ;

Shimada, Shigeru .

CHEMISTRY-AN ASIAN JOURNAL, 2011, 6 (09) :2512-2521

[9]

Frech C. M., 2005, ANGEW CHEM, V117, p1737

[10] Redox-induced collapse and regeneration of a pincer-type complex framework: A nonplanar coordination mode of palladium(II) [J].

Frech, CM ;

Shimon, LJW ;

Milstein, D .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (11) :1709-1711

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