Methylation of a terdentate Schiff base ligand NNO-coordinated to palladium with nitromethane

被引：6

作者：

Arnaiz, Ana M. ^{[1
]}

Carbayo, Arancha ^{[1
]}

Cuevas, Jose V. ^{[1
]}

Diez, Virginia ^{[1
]}

Garcia-Herbosa, Gabriel ^{[1
]}

González, Roberto ^{[1
]}

Martinez, Abigail ^{[1
]}

Munoz, Asuncion ^{[1
]}

机构：

[1] Univ Burgos, Dept Quim, Burgos 09001, Spain

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2007年 / 29期

关键词：

palladium; Henry reaction; nucleophilic attack; nitroaldol; Schiff bases;

D O I：

10.1002/ejic.200700469

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The reaction of the complex [Pd(kappa(3)-NN'O)CH3] [NN'O = 2Py-CH=N-(o-C6H4)O-] (1a) with nitromethane affords a mixture of 2a and 2b. In this reaction methylation of the ligand takes place. These complexes display exchange equilibrium in solution. The methylation reaction is proposed to occur through nucleophilic attack of the nitronate anion on the iminic carbon atom. DFT calculations are presented in order to support a part of the mechanism and these calculations show that the participation of water in the migration of a proton is important. The crystal structure of the derivative product after spontaneous release of methane (3) is presented as well. Attempts to extend the reaction to other nitroalkanes resulted in a mixture of complexes that was not easy to characterize.

引用

页码：4637 / 4644

页数：8

共 53 条

[1]

[Anonymous], 1992, INT TABLES CRYSTALLO, VC

[2] Revealing the diastereomeric nature of pincer terdentate nitrogen ligands 2,6-bis(arylaminomethyl)pyridine through coordination to palladium [J].