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环戊二烯基钌（II）与三（烷硫基）苯配合物的合成与反应性：双核与夹心型配合物之间的转变

Synthesis and Reactivity of Cyclopentadienyl Ruthenium(II) Complexes with Tris(alkylthio)benzenes: Transformation between Dinuclear and Sandwich-Type Complexes.

作者信息

Fan Rong, Sumitani Ryo, Mochida Tomoyuki

机构信息

Department of Chemistry, Graduate School of Science, Kobe University, Rokkodai, Kobe, Hyogo 657-8501, Japan.

Center for Membrane and Film Technology, Kobe University, Rokkodai, Nada, Kobe, Hyogo 657-8501, Japan.

出版信息

ACS Omega. 2020 Jan 23;5(4):2034-2040. doi: 10.1021/acsomega.9b04272. eCollection 2020 Feb 4.

DOI:10.1021/acsomega.9b04272
PMID:32039341
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7003506/
Abstract

To explore the structural transformation of cyclopentadienyl ruthenium (CpRu) complexes in response to external stimuli, the reaction of [RuCp(MeCN)][X] (X = PF, (FSO)N [= FSA]) and tris(alkylthio)benzenes (1,3,5-CH(SR); : R = Pr, : R = Me) was investigated, and the crystal structures and thermal properties of the products were examined. The reaction produced the sandwich complexes [RuCp ][X] or dinuclear complexes [RuCp(μ- )(CHCN) ][X] (X = PF, FSA) depending on the reaction conditions. The sandwich complex [RuCp ][FSA] was an ionic liquid. The solids of dinuclear complexes transformed into the thermodynamically stable sandwich complexes upon heating accompanied by acetonitrile loss. This change resulted in a transformation from crystal to ionic liquid for complexes with the FSA anion. UV irradiation of the sandwich complex [RuCp ][PF] in methanol produced the dinuclear complex [RuCp(μ- ) ][PF]. The complex transformed into the sandwich complex upon heating.

摘要

为了探究环戊二烯基钌（CpRu）配合物响应外部刺激的结构转变，研究了[RuCp(MeCN)][X]（X = PF，(FSO)N [= FSA]）与三（烷硫基）苯（1,3,5-CH(SR); ：R = Pr， ：R = Me）的反应，并考察了产物的晶体结构和热性质。根据反应条件，该反应生成了夹心配合物[RuCp ][X]或双核配合物[RuCp(μ - )(CHCN) ][X]（X = PF，FSA）。夹心配合物[RuCp ][FSA]是一种离子液体。双核配合物的固体在加热时伴随着乙腈的损失转化为热力学稳定的夹心配合物。这种变化导致具有FSA阴离子的配合物从晶体转变为离子液体。夹心配合物[RuCp ][PF]在甲醇中经紫外线照射生成双核配合物[RuCp(μ - ) ][PF]。该配合物在加热时转化为夹心配合物。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1806/7003506/ce2737b7cc66/ao9b04272_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1806/7003506/cf6225bdd802/ao9b04272_0001.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1806/7003506/f282bf97986c/ao9b04272_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1806/7003506/321f80925676/ao9b04272_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1806/7003506/dae8bc86d693/ao9b04272_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1806/7003506/a120052df74e/ao9b04272_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1806/7003506/ce2737b7cc66/ao9b04272_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1806/7003506/cf6225bdd802/ao9b04272_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1806/7003506/63be851a0e54/ao9b04272_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1806/7003506/acd4e07b1b25/ao9b04272_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1806/7003506/834f2f6ac52c/ao9b04272_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1806/7003506/f282bf97986c/ao9b04272_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1806/7003506/321f80925676/ao9b04272_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1806/7003506/dae8bc86d693/ao9b04272_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1806/7003506/a120052df74e/ao9b04272_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1806/7003506/ce2737b7cc66/ao9b04272_0009.jpg

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