<![CDATA[Deviation from the trans-Effect in Ligand-Exchange Reactions of Zeise’s Ions PtCl3(C2H4)? with Heavier Halides (Br–, I–)]]>

Gao-Lei Hou; Niranjan Govind; Sotiris S. Xantheas; Xue-Bin Wang

首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >3(C₂H₄)? with Heavier Halides (Br–, I–)]]>

【24h】

3(C₂H₄)? with Heavier Halides (Br–, I–)]]>

机译：<！[CDATA [偏离反式 - 在Zeise离子的配体交换反应中，Ptcl _{3 （c _{2 h _{4 ）？，具有较重的卤化物（br - ，i - ）]]>}}}

获取原文

获取原文并翻译 | 示例

掌桥外文数据库（机构版） >>

开具论文收录证明 >>

文献代查 >>

页面导航

摘要
著录项
相似文献
相关主题

摘要

Four new Zeise’s family ions with mixed-halide ligands, i.e., PtCl_( n )X_(3– n )(C_(2)H_(4))~(?) (X = Br, I; n = 1, 2), were synthesized via ligand-exchange reactions of KX salts with KPtCl_(3)(C_(2)H_(4)) in aqueous solutions, and were detected in vacuum via electrospray ionization mass spectrometry. Their photoelectron spectra reveal a series of well-resolved spectral peaks with their electron binding energies (EBEs) decreasing with increasing halide size, with I having a much stronger effect than Br, i.e., 4.57 (?Cl_(3)) > 4.56 (?Cl_(2)Br) > 4.53 (?ClBr_(2)) > 4.34 (?Cl_(2)I) > 4.30 eV (?ClI_(2)). Ab initio electronic structure calculations including spin–orbit coupling (SOC) predict that the cis - and trans -isomers are nearly isoenergetic with the cis -isomer for ?Cl_(2)X and the trans -isomer for ?ClX_(2) slightly favored, respectively. Excited-state spectra calculated with time-dependent density functional theory (TDDFT), and their comparison with the observed ones, suggest that for each species both the cis - and trans -configurations coexist in the experiments and contribute to the observed spectra, a fact that clearly deviates from the prediction of the widely accepted trans -effect, which suggests that only one isomer would have formed.

机译：四种新的Zeise的家族离子，其中卤化卤配体，即PtCl_（n）X_（3-N）（C_（2）H_（4））〜（？）（x = Br，i; n = 1,2），通过Kx Salts的配体 - 交换反应与水溶液中的KPTCl_（3）（C_（2）H_（4））合成，并通过电喷雾电离质谱法真空检测。它们的光电子光谱显示出一系列良好的分辨光谱峰，其电子结合能量（EBES）随着卤化物尺寸的增加而降低，其具有比BR的更强的效果，即4.57（ΔCl_（3））> 4.56（？ CL_（2）BR）> 4.53（？CLBR_（2））> 4.34（？CL_（2）I）> 4.30eV（？CLI_（2））。 AB Initio电子结构计算，包括旋转轨道耦合（SoC）预测CIS - 和反式分子与CIS-isOmer几乎是ΔCL_（2）x和旋转异构体的异晶体。（2）略微青睐，分别。随着时间依赖性密度泛函理论（TDDFT）计算的激发状态光谱及其与观察到的思想的比较，表明，对于每个物种，CIS - 和Trans-Configurations都在实验中共存并有助于观察到的光谱，这是一个事实这清楚地偏离了广泛接受的跨越的预测，这表明只有一个异构体形成。

著录项

来源
《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2018年第5期|共6页
作者
Gao-Lei Hou; Niranjan Govind; Sotiris S. Xantheas; Xue-Bin Wang;
展开▼
作者单位

Physical and Computational Sciences Directorate Pacific Northwest National Laboratory 902 Battelle Boulevard P.O. Box 999 MS K8-88 Richland Washington 99352 United States;

Environmental Molecular Sciences Laboratory Pacific Northwest National Laboratory P.O. Box 999 MS K8-91 Richland Washington 99352 United States;

Advanced Computing Mathematics and Data Division Pacific Northwest National Laboratory 902 Battelle Boulevard P.O. Box 999 MS K1-83 Richland Washington 99352 United States;

Physical and Computational Sciences Directorate Pacific Northwest National Laboratory 902 Battelle Boulevard P.O. Box 999 MS K8-88 Richland Washington 99352 United States;

展开▼
收录信息
原文格式 PDF
正文语种 eng
中图分类物理化学（理论化学）、化学物理学;
关键词

相似文献

外文文献
中文文献
专利

1. 3(C₂H₄)? with Heavier Halides (Br–, I–)]]> [J] . Gao-Lei Hou, Niranjan Govind, Sotiris S. Xantheas, The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2018,第5期

机译：<！[CDATA [偏离反式 - 在Zeise离子的配体交换反应中，Ptcl _{3 （c _{2 h _{4 ）？，具有较重的卤化物（br - ，i - ）]]>}}}
2. Modulation of properties in analogues of Zeise's anion on changing the ligand trans to ethene. X-Ray crystal structures of trans-[PtCl _2(OH)(η ~2-C _2H _4)] ~- and trans-[PtCl _2(η ~1-CH _2NO _2) (η ~2-C _2H _4)] ~- [J] . Benedetti M., Barone C.R., Antonucci D., Dalton transactions: An international journal of inorganic chemistry . 2012,第10期

机译：Zeise阴离子类似物对将配体反式转变为乙烯的性质的调节。反式-[PtCl _2（OH）（η〜2-C _2H _4）]〜-和反式-[PtCl _2（η〜1-CH _2NO _2）（η〜2-C _2H _4）的X射线晶体结构]〜-
3. [(C_2H_4)PtCl_3]~-, the Anion of Zeise's Salt, K[C_2H_4)PtCl_3]·H_2O [J] . Dietmar Seyferth Organometallics . 2001,第1期

机译：[（C_2H_4）PtCl_3]〜-蔡斯盐的阴离子，K [C_2H_4）PtCl_3]·H_2O
4. Emission Mechanism Switching of Luminescent Re(V) Complexvia Ligand-exchange Reaction in Solid-gas Interface [C] . Kenta Sasaki, Hitomi Yamate, HarukaYoshino 日本化学会春季年会 . 2020

机译：固体气体界面中发光Re（v）复合体配体交换反应的发射机理切换
5. XPS studies of alkali halogen oxides, ozone exposure to alkali halides and halate-halide reactions in thin-film water. [D] . Newberg, John T. 2005

机译：XPS研究了薄膜水中的碱金属卤氧化物，臭氧暴露于碱金属卤化物和卤化物-卤化物反应。
6. Highly Tunable Emission by Halide Engineering in Lead-Free Perovskite-Derivative Nanocrystals: The Cs2SnX6 (X = Cl Br Br/I I) System [O] . Alessandro Veronese, Maddalena Patrini, Daniele Bajoni, 2020

机译：无卤钙钛矿衍生物纳米晶体中卤化物工程的高度可调发射：Cs2SnX6（X = ClBrBr / II）系统
7. Erratum: Cyclobutadiene–metal complexes. Part VIII. Synthesis of tetraphenylcyclobutadienenickel halides by ligand-exchange reactions [O] . D. F. Pollock, P. M. Maitlis 1967

机译：错误：环丁二烯 - 金属配合物。第VIII部分。通过配体交换反应合成四苯基环丁二烯尼尼酸卤化物

3(C2H4)? with Heavier Halides (Br–, I–)]]>

摘要

著录项

相似文献

相关主题

期刊订阅

3(C₂H₄)? with Heavier Halides (Br–, I–)]]>