Exceptionally facile CO addition to a saturated ruthenium complex

被引：18

作者：

Bibal, C

Smurnyy, YD

Pink, M

Caulton, KG ^{[1
]}

机构：

[1] Indiana Univ, Dept Chem, Bloomington, IN 47405 USA

[2] Indiana Univ, Ctr Mol Struct, Bloomington, IN 47405 USA

[3] Moscow MV Lomonosov State Univ, Dept Chem, Moscow 199992, Russia

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2005年 / 127卷 / 25期

关键词：

D O I：

10.1021/ja051296h

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Synthesis and characterization of Cp*Ru[η3-HC(PPh2NPh)2], 1, reveals it to have a "piano stool" structure with the ligand bound to Ru(II) via two N and the unique, sp3 hybridized carbon. While the analogous (cymene) Ru[η3-HC(PPh2NPh)2]+ does not react with CO, under the same conditions, 1 adds one CO rapidly (25 °C, 1 atm CO). Characterization, including an X-ray structure determination, shows that CO has displaced one chelate ligand nitrogen, which then hangs off the molecule, free of Ru. DFT calculations reveal a possible mechanism via a remarkably low energy (+9.3 kcal/mol) intermediate, pendant N, but with one phenyl on phosphorus stabilizing Ru via donation from a C(ipso)=C(ortho) bond. DFT calculations show that the electronic energy change for binding CO is over 20 kcal/mol less favorable for cymene than for C5Me5- as ligand; the reactivity difference is thus thermodynamic in origin. Copyright © 2005 American Chemical Society.

引用

页码：8944 / 8945

页数：2

共 19 条

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