期刊
JOURNAL OF ORGANOMETALLIC CHEMISTRY
卷 880, 期 -, 页码 232-240出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jorganchem.2018.11.002
关键词
Platinum; N-methylation; Oxidative addition; DFT calculation; Kinetic and mechanism
资金
- Center for Scientific Computing from the CNSI
- MRL: an NSF MRSEC [DMR-1121053]
- NSF [CNS-0960316]
- Shiraz University
- Department of Chemistry and Biochemistry at UCSB
The new cyclometalated platinum(II) complexes [PtMe((CN)-N-boolean AND)(pyrazine)] [(CN)-N-boolean AND = benzo[h] quinolate (bhq), 1a; (CN)-N-boolean AND = 2-phenylpyridinate (ppy), 1c] have been prepared by the reaction of corresponding dimethylsulfide complexes with pyrazine. These complexes contain two potential nucleophilic centers, Pt(II) center and free N atom of pyrazine which can compete in the reaction with methyl iodide to give Pt(IV) oxidative addition or N-methylation products, respectively. To investigate which center is more reactive toward MeI, DFT calculations (based on the free energy barrier needed for N-methylation versus oxidative addition reactions) and experimental evidence is considered to predict and explain site selectivity. Both experimental and theoretical studies show that the oxidative addition of MeI to cyclometalated Pt(II) complexes occurs readily to give the Pt(IV) complexes. Theoretical results support remarkably the kinetic results obtained through UV-Vis spectroscopy which suggest an S(N)2 mechanism. (C) 2018 Elsevier B.V. All rights reserved.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据