Reactivity Studies of [(thf)(2)Mg{mu-C(CH3)(2)C2H4C(CH3)(2)}](2): Scrambling Reactions and Diverse Reactions with Dichlorophenylphosphane

Fischer Reinald; Gorls Helmar; Westerhausen Matthias

首页> 外文期刊>Organometallics >Reactivity Studies of [(thf)(2)Mg{mu-C(CH3)(2)C2H4C(CH3)(2)}](2): Scrambling Reactions and Diverse Reactions with Dichlorophenylphosphane

【24h】

Reactivity Studies of [(thf)(2)Mg{mu-C(CH3)(2)C2H4C(CH3)(2)}](2): Scrambling Reactions and Diverse Reactions with Dichlorophenylphosphane

机译：[（thf）（2）Mg {mu-C（CH3）（2）C2H4C（CH3）（2）}]（2）的反应性研究：加二氯苯基膦的加扰反应和不同反应

获取原文

获取原文并翻译 | 示例

获取外文期刊封面封底 >>

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

In THF solution [{(thf)(2)Mg{mu-C(CH3)(2)C2H4(CH3)(2)C}}(2)] (1) exchanges the alkanediide ligand with [{(thf)(2)Mg{mu-CH2)(5)}}(2)] in an equilibrium leading to the formation of (thf)(2)Mg}(2){mu-C(CH3)(2)C2H4C(CH3)(2)}{mu-(CH2)(5)}] (2). Depending on the crystallization temperature, homoleptic 1 or heteroleptic 2 crystallizes from THF solutions, verifying a temperature-dependent Schlenk equilibrium. Irradiation of a solution of 1 in [D-8]THF with UV light yields magnesium hydride and alkene via a beta-hydride elimination reaction. In a metathetical approach dichlorophenylphosphane reacts with 1 in THF to give the intermediate "PhP(CI){C(CH3)(2)C2H4(CH3)(2)CMgCl" (3-MgCl), which forms three subsequent products. In order to ease handling and characterization of these compounds, hydrolysis and oxidation with sulfur has been performed. This product mixture was separated by column chromatography, yielding the chlorophosphane sulfide [Ph(S)P(Cl){C(CH3)(2)C2H4(CH3)(2)CH)}] (3-S), the cyclic phosphane sulfide [Ph(S)P{C(CH3)(2)C2H4(CH3)(2)C)}] (4-S), and the cyclic 1,1-diphosphane disulfide [{(Ph(S)P}(2){mu-C(CH3)(2)C2H4(CH3)(2)C}] (6-S-2). Furthermore, traces of the acyclic 1,1-diphosphane disulfides [{PhP(S)(C(CH3)(2)C2H4CH(CH3)(2))}{PhP(S)(C(CH3)(2)C2H4C(CH3)(CH2)}] (8-S-2) and meso-[{Ph(S)P(C(CH3)(2)C2H4(CH3)(2)CH)}(2)] (7-S-2) have also been isolated. Compounds 6-8 represent the phosphorus-containing products of indirect Grignard reductions.

机译：在THF溶液中[{{（thf）（2）Mg {mu-C（CH3）（2）C2H4（CH3）（2）C}}（2）]（1）将烷二酰亚胺配体与[{ 2）Mg {mu-CH2）（5）}}（2）]处于平衡状态，导致形成（thf）（2）Mg}（2）{mu-C（CH3）（2）C2H4C（CH3）（2）} {mu-（CH2）（5）}]（2）。取决于结晶温度，均熔剂1或杂合剂2从THF溶液中结晶，从而验证了温度相关的Schlenk平衡。用紫外线照射1在[D-8] THF中的溶液，通过β-氢化物消除反应生成氢化镁和烯烃。在一种复分解方法中，二氯苯基膦与THF中的1反应生成中间体“ PhP（Cl）{C（CH3）（2）C2H4（CH3）（2）CMgCl”（3-MgCl），形成了三个后续产物。为了简化这些化合物的处理和表征，已经进行了用硫进行的水解和氧化。通过柱色谱分离该产物混合物，得到氯膦硫化物[Ph（S）P（Cl）{C（CH3）（2）C2H4（CH3）（2）CH）}]（3-S），环膦硫化物[Ph（S）P {C（CH3）（2）C2H4（CH3）（2）C）}]（4-S）和环状1,1-二膦二硫化物[{（Ph（S）P} （2）{mu-C（CH3）（2）C2H4（CH3）（2）C}]（6-S-2）。此外，还有痕量的无环1,1-二膦二硫化物[{PhP（S）（ C（CH3）（2）C2H4CH（CH3）（2））} {PhP（S）（C（CH3）（2）C2H4C（CH3）（CH2）}]（8-S-2）和内消旋[{还分离了Ph（S）P（C（CH3）（2）C2H4（CH3）（2）CH）}（2）]（7-S-2）。化合物6-8代表间接格氏减少量。

著录项

来源
《Organometallics》 |2016年第22期|共9页
作者
Fischer Reinald; Gorls Helmar; Westerhausen Matthias;
展开▼
作者单位

展开▼
收录信息
原文格式 PDF
正文语种 eng
中图分类
关键词

相似文献

外文文献
中文文献
专利

1. Reactivity Studies of [(thf)(2)Mg{mu-C(CH3)(2)C2H4C(CH3)(2)}](2): Scrambling Reactions and Diverse Reactions with Dichlorophenylphosphane [J] . Fischer Reinald, Gorls Helmar, Westerhausen Matthias Organometallics . 2016,第22期

机译：[（thf）（2）Mg {mu-C（CH3）（2）C2H4C（CH3）（2）}]（2）的反应性研究：加二氯苯基膦的加扰反应和不同反应
2. Molecular Dynamics of Combustion Reactions in Supercritical Carbon Dioxide. Part 5: Computational Study of Ethane Dissociation and Recombination Reactions C2H6 (sic) CH3 + CH3 [J] . Wang Chun-Hung, Panteleev Sergey V, Masunov Artem E., The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2019,第22期

机译：超临界二氧化碳中燃烧反应的分子动力学。第5部分：乙烷解离和重组反应的计算研究C2H6（SiC）CH3 + CH3
3. Synthesis and structural study of the ate-complex rac-(CH3)(2)C(C5H3-3-Si(CH3)(3))(2)Yb(mu(2)-Cl)(2)Li(OEt2)(2) and the polymeric compound {rac-(CH3)(2)C(C5H3-3-Si(CH3)(3))(2)Yb[(mu(2)-H)(2)B(mu(2)-H)(2)](2)Li(THF )(2)}(infinity) [J] . Khvostov AV., Sizov AI., Bulychev BM., Journal of Organometallic Chemistry . 1998,第1a2期

机译：复杂配合物rac-（CH3）（2）C（C5H3-3-Si（CH3）（3））（2）Yb（mu（2）-Cl）（2）Li（OEt2）的合成和结构研究（2）和高分子化合物{rac-（CH3）（2）C（C5H3-3-Si（CH3）（3））（2）Yb [（mu（2）-H）（2）B（mu（ 2）-H）（2）]（2）Li（THF）（2）}（无穷大）
4. Reaction paths, kinetics and thermochemical properties on reaction of methylthiyl (CH3S)and methylthiomethyl (CH3SCH3) radicals with O2 [C] . Fei Jin, Li Zhu, Joseph W. Bozzelli Fourth Joint Meeting of the U.S. Sections of the Combustion Institute: Western States, Central States, Eastern States: Abstracts . 2005

机译：甲基噻吩（CH3S）和甲基硫代甲基（CH3SCH3）与O2反应的反应路径，动力学和热化学性质
5. Reaction Chemistry of the Heavier Group 14 Carbene Analogues, M[Ar(Me6)]2, with Small Molecules Mediated by Synergistic Effects (M=Germanium, Tin; Ar(Me6)=C6H3-2,6-(C6H2-2,4,6-(CH3)3)2). [D] . Brown, Zachary Douglas. 2012

机译：重型14类羰基化合物M [Ar（Me6）] 2与小分子通过协同效应介导的反应化学（M =锗，锡; Ar（Me6）= C6H3-2,6-（C6H2-2,4 ，6-（CH3）3）2）。
6. Attempted hydrogen–deuterium exchange of the protio-trimethyloxonium dication (CH3)3OH2+ study of methylating ability of (CH3)3O+ in superacids and theoretical investigations [O] . George A. Olah, Golam Rasul, Arwed Burrichter, 1998

机译：尝试氢-氘交换原三甲基氧鎓离子（CH3）3OH2 +研究（CH3）3O +在超强酸中的甲基化能力和理论研究
7. Reactivity Studies of (thf)2Mg{-C(CH3)2C2H4C(CH3)2}2: Scrambling Reactions and Diverse Reactions with Dichlorophenylphosphane [O] . -1

机译：（THF）2mg {-C（CH3）2C2H4C（CH3）2} 2的反应性研究2：加扰反应和与二氯苯基膦的多种反应
8. Reactions of CH3 OH2 (+), CH3 OH2 (+) .CH3 OH, and (CH3)2 PH (+) with Methanol:Effect of Solvation [R] . Morris, R. A., Viggiano, A. A., Paulson, J. F., 1992

机译：CH3OH2（+），CH3OH2（+）。CH3OH和（CH3）2 pH（+）与甲醇的反应：溶剂化的影响

Reactivity Studies of [(thf)(2)Mg{mu-C(CH3)(2)C2H4C(CH3)(2)}](2): Scrambling Reactions and Diverse Reactions with Dichlorophenylphosphane

摘要

著录项

相似文献

相关主题

期刊订阅