Behavior of the bischelate platinum(II) complexes [Pt(S^N)(C^N)] (S^N = pyridine-2-thionate, C^N = 2-phenylpyridinate or benzo[h]quinolate) toward C-I bond activation; a DFT study

被引：0

作者：

Darani F.A. ^{[1
]}

Esmaeilbeig A.R. ^{[1
]}

Hosseini F.N. ^{[2
]}

Nabavizadeh S.M. ^{[1
]}

机构：

[1] Department of Chemistry, College of Sciences, Shiraz University, Shiraz

[2] Department of Chemistry, Shiraz Branch, Islamic Azad University, Shiraz

来源：

Structural Chemistry | 2015年 / 26卷 / 4期

基金：

美国国家科学基金会;

关键词：

Bischelate; C-I bond activation; Cycloplatinated complexes; DFT study; Pyridine-2-thionate;

D O I：

10.1007/s11224-014-0555-7

中图分类号：

学科分类号：

摘要：

Abstract The oxidative addition reactions of RI (R = CH3 or C2H5) to the [Pt(S^N)(C^N)] complexes (S^N = pyridine-2-thionate, C^N = 2-phenylpyridinate or benzo[h]quinolate) were theoretically investigated using density functional theory calculations to gain more insight into the mechanism of the reactions, as well as to try and determine the geometry of the transition states and energy barriers. The DFT study suggested the formation of transition states including Pt...C(R)...I fragments, followed by the formation of the ionic five-coordinate [PtR(S^N)(C^N)]+I- intermediates with the R group in the apical position and with the iodide ion out of coordination sphere of Pt center. The DFT studies were in agreement with the experimental finding and showed that the nature of R group in alkyl halide had a significant influence on the energy barriers of the reactions, but the nature of C^N chelate ligand does not change significantly the energy barrier of oxidative addition when R is constant. © 2014 Springer Science+Business Media New York.

引用

页码：961 / 969

页数：8

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