Unsymmetrical bidentate ligands of α-aminoaldimines leading to sterically controlled selectivity of geometrical isomerism in square planar coordination

被引：14

作者：

Lee, Jen-Jeh ^{[1
]}

Yang, Feng-Zhao ^{[1
]}

Lin, Ya-Fan ^{[1
]}

Chang, Ya-Chun ^{[1
]}

Yu, Kuo-Hsuan ^{[1
]}

Chang, Mu-Chieh ^{[1
]}

Lee, Gene-Hsiang ^{[1
]}

Liu, Yi-Hung ^{[1
]}

Wang, Yu ^{[1
]}

Liu, Shiuh-Tzung ^{[1
]}

Chen, Jwu-Ting ^{[1
]}

机构：

[1] Natl Taiwan Univ, Dept Chem, Taipei 106, Taiwan

来源：

DALTON TRANSACTIONS | 2008年 / 43期

关键词：

D O I：

10.1039/b805674a

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

New alpha-aminoaldimines with the formula of Et(2)NCMe(2)CH=NR (R = (i)Pr, (t)Bu, Ph) and their dichloro or diacetato complexes of Ni, Pd, Pt are prepared and structurally characterized. A nickel complex is in a distorted tetrahedral configuration, and the Pd and Pt complexes (4-6) are of square planar form. The alpha-aminoaldimines can chelate to the metal in a C(2)-unsymmetric bidentate motif through the hetero functionalities of amine and imine, which show comparable trans influence. Square planar organometallic palladium derivatives bearing alpha-aminoaldimines, including Pd-methyl, Pd-acetyl, and Pd-(eta(2)-acetylnorboryl) (7-10), are also synthesized. The latter two species are a result of CO-insertion into Pd-methyl complexes and ensuing norbornene-insertion, respectively. The geometrical isomerism is found in the trans configuration in most studied cases. Such a stereoselectivity results from the thermodynamic stability governed predominantly by steric control. The stereoselectivity is also supported by DFT calculations.

引用

页码：5945 / 5956

页数：12

共 103 条

[1]

Agostinho M, 2007, DALTON T, P759, DOI 10.1039/b616962g

[2] CARBONYL-INSERTION REACTIONS OF SQUARE-PLANAR COMPLEXES [J].