Unexpected rearrangement of 4-chloro-2-butenylphosphinidene to 1-chloro-2-vinylphosphirane in the coordination sphere of tungsten

Huy NHT; Gryaznova TV; Ricard L; Mathey F

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Unexpected rearrangement of 4-chloro-2-butenylphosphinidene to 1-chloro-2-vinylphosphirane in the coordination sphere of tungsten

机译：钨配位球中4-氯-2-丁烯基次膦发生意外的重排成1-氯-2-乙烯基膦烷

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The complex (4-chloro-2-butenylphosphinidene)pentacarbonyltungsten, as generated from the appropriate 7-phosphanorbornadiene complex at 58 degrees C in the presence of copper(1) chloride as a catalyst, readily rearranges to give the stable 1-chloro-2-vinylphosphirane complex. According to DFT calculations on similar Cr(CO)(5) complexes, a concerted six-electron (sigma C-Cl bond, P lone pair, and pi C=C double bond), five-center mechanism could be involved with a low energy barrier of 4.8 kcal mol(-1) in the chromium series.

机译：在适当的条件下，由适当的7-膦基降冰片二烯络合物在58℃下在氯化铜（1）作为催化剂的条件下生成的络合物（4-氯-2-丁烯基次膦基）五羰基钨容易重排，得到稳定的1-氯-2 -乙烯基膦烷配合物。根据对相似的Cr（CO）（5）配合物的DFT计算，六电子（σC-Cl键，P lone对和pi C = C双键）协调一致，可能涉及低价位的五中心机理铬系列中4.8 kcal mol（-1）的能垒。

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来源
《Organometallics》 |2005年第12期|共5页
作者
Huy NHT; Gryaznova TV; Ricard L; Mathey F;
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正文语种 eng
中图分类有机化学;
关键词
TERMINAL PHOSPHINIDENE COMPLEX; RAY CRYSTAL-STRUCTURE; DOUBLE-BOND; CHEMISTRY; STABILIZATION; ACTIVATION; DENSITY;

机译：终端膦化合物;射线晶体结构;双键;化学;稳定化;活化;密度;

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1. Unexpected rearrangement of 4-chloro-2-butenylphosphinidene to 1-chloro-2-vinylphosphirane in the coordination sphere of tungsten [J] . Huy NHT, Gryaznova TV, Ricard L, Organometallics . 2005,第12期

机译：钨配位球中4-氯-2-丁烯基次膦发生意外的重排成1-氯-2-乙烯基膦烷
2. Unexpected Trimerization of Pyrazine in the Coordination Sphere of Low-Valent Titanocene Fragments [J] . Thomas Jung, Rudiger Beckhaus, Thorsten Kluner Journal of chemical theory and computation: JCTC . 2009,第8期

机译：低价二茂钛片段配位域中吡嗪的意外三聚化
3. Unexpected Transformations of O~(2-), O_2~(2-), and O_3~(2-) Ligands in the Vanadium(V) Coordination Sphere: Quantum-Chemical Modeling [J] . A. A. Markov, S. P. Dolin, N. I. Moiseeva Doklady Physical Chemistry . 2009,第1期

机译：钒（V）配位域中O〜（2-），O_2〜（2-）和O_3〜（2-）配体的意外转变：量子化学建模
4. Reaction of α-Imino Thioesters and the Subsequent C-C Bond Formation with the Unexpected Alkylthio Rearrangement [C] . Isao Mizota, Makoto Shimizu 日本化学会春季年会講演予稿集 . 2018

机译：α-氨基氨基氨基氨基铵和随后的C-C键形成与意外的烷硫基重排反应
5. Ligand based reactions in the chiral tungsten fragment coordination sphere. [D] . Vogeley, Neil J. 2004

机译：手性钨碎片配位域中基于配体的反应。
6. The reaction mechanism of the enantioselective Tsuji allylation: inner-sphere and outer-sphere pathways internal rearrangements and asymmetric C–C bond formation [O] . John A. Keith, Douglas C. Behenna, Nathaniel Sherden, -1

机译：对映选择性的Tsuji烯化的反应机制：内球和外球途径内部重排和不对称C-C键形成
7. Unexpected Rearrangement of 4-Chloro-2-butenylphosphinidene to 1-Chloro-2-vinylphosphirane in the Coordination Sphere of Tungsten [O] . -1

机译：在钨的协调球体中出现意外重新排列4-氯-2-丁苯基氨基氨基至1-氯-2-乙烯基磷酸盐
8. Organosilicon Rotanes. Synthesis and an Unexpected Rearrangement. [R] . Carlson, C. W., Zhang, X. H., West, R. 1982

机译：有机硅旋转。合成和意外重排。

Unexpected rearrangement of 4-chloro-2-butenylphosphinidene to 1-chloro-2-vinylphosphirane in the coordination sphere of tungsten

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