由同手性四膦支撑的钯链中，手性四钯单元之间的手性自识别。
Chiral Self-Recognition between Stereogenic Tetrapalladium Units Affording Pd Chains Supported by Homochiral Tetraphosphines.
作者信息
Tanase Tomoaki, Morita Konomi, Otaki Risa, Yamamoto Kana, Kaneko Yukino, Nakamae Kanako, Kure Bunsho, Nakajima Takayuki
机构信息
Department of Chemistry, Faculty of Science, Nara Women's University, Kitauoya-nishi-machi, Nara, 630-8506, Japan.
出版信息
Chemistry. 2017 Jan 12;23(3):524-528. doi: 10.1002/chem.201605146. Epub 2016 Nov 22.
By using a chiral tetraphosphine, rac-bis[(diphenylphosphinomethyl)phenylphosphino]methane (rac-dpmppm), linear octapalladium chains were synthesized as discrete molecules of Pd (μ-rac-dpmppm) L (L=CH CN, dmf, XylNC), Pd (μ-rac-dpmppm) , and Pd (μ-rac-dpmppm) (Cl) , which are stable in the solution states and characterized by spectroscopic and crystallographic methods to reveal the octapalladium chains supported by homochiral four tetraphosphines. Variable-temperature NMR studies for a 1:1 mixture of Pd (μ-rac-dpmppm) (dmf) and [Pd (μ-meso-dpmppm) (dmf) ]-(BF ) in [D ]DMF revealed that the Pd chains were dissociated at higher temperature (T≈140 °C) into the Pd units of {Pd (μ-rac-dpmppm) } and {Pd (μ-meso-dpmppm) } , and they were thermodynamically self-aligned to restore the Pd chains at lower temperature (T<60 °C), through perfect chiral self-recognition between the stereogenic tetrapalladium units.
通过使用手性四膦，即外消旋双[（二苯基膦甲基）苯基膦基]甲烷（外消旋-dpmppm），合成了线性八钯链，其为离散分子Pd(μ-外消旋-dpmppm)L（L = CH₃CN、dmf、XylNC）、Pd(μ-外消旋-dpmppm)以及Pd(μ-外消旋-dpmppm)(Cl)，这些分子在溶液状态下稳定，并通过光谱和晶体学方法进行表征，以揭示由同手性四个四膦支撑的八钯链。对Pd(μ-外消旋-dpmppm)(dmf)和[Pd(μ-内消旋-dpmppm)(dmf)]-(BF₄)在[D₈]DMF中的1:1混合物进行变温核磁共振研究表明，钯链在较高温度（T≈140 °C）下解离为{Pd(μ-外消旋-dpmppm)}和{Pd(μ-内消旋-dpmppm)}的钯单元，并且它们在较低温度（T<60 °C）下通过立体异构四钯单元之间完美的手性自识别进行热力学自排列以恢复钯链。
Zotero 插件