Reversible Stereoisomerization of 1,3-Diphosphetane Frameworks Revealed by a Single-Electron Redox Approach

Chen，Xiaodan1; Hu，Chenyang2; Zhang，Xu1; Liu，Shihua3; Mei，Yanbo2; Hu，Guping3; Liu，Liu Leo2; Li，Zhongshu1,3; Su，Cheng Yong3

2021

10.1021/acs.inorgchem.1c00064

INORGANIC CHEMISTRY   影响因子和分区

0020-1669

1520-510X

The discovery of pyramidal inversion has continued to impact modern organic and organometallic chemistry. Sequential alkylation reactions of an N-heterocyclic carbene (NHC) ligated dicarbondiphosphide 1 with RI (R = Me, Et, or iBu) and ZnMe2 give rise to the highly stereoselective synthesis of cis-1,3-diphosphetanes 3. cis-3 is conformationally favorable at room temperature, whereas inversion to trans-3 is observed at 110 °C. One-electron oxidation of cis-3 with Fc+(BArF) (Fc = [Fe(C5H5)2]; BArF = [B(3,5-(CF3)2C6H3)4)]-) leads to the stereoselective formation of trans-1,3-diphosphetane radical cation salts 3•+(BArF), which can be reversibly transformed to cis-3 upon one-electron reduction. Salts 3•+(BArF) represent the first examples of 1,3-diphosphetane radical cations. These results provide a potential application of planar four-membered heterocycle-based building blocks for electrically fueled molecular switches.

SCI ; EI

英语

NI期刊

其他

National Natural Science Foundation of China[21703084,21720102007] ; Tip-top Scientific and Technical Innovative Youth Talents of Guangdong Special Support Program[2019TQ05C926] ; Open Fund of Guangdong Provincial Key Laboratory of Functional Supramolecular Coordination Materials and Applications[2020A04] ; SUSTech start-up fund[Y01216248]

Chemistry

Chemistry, Inorganic & Nuclear

WOS:000642344900038

AMER CHEMICAL SOC

20211810291888

Organometallics ; Positive ions ; Salts ; Stereochemistry ; Stereoselectivity ; Synthesis (chemical)

Chemistry:801 ; Chemical Reactions:802.2 ; Organic Compounds:804.1

CHEMISTRY

2-s2.0-85104915336

Scopus

1.Guangdong Prov. Key Laboratory of Functional Supramolecular Coordination Materials and Applications,College of Chemistry and Materials Science,Jinan University,Guangzhou,510632,China
2.Shenzhen Grubbs Institute and Department of Chemistry,Southern University of Science and Technology,Shenzhen,518055,China
3.Lehn Institute of Functional Materials (LIFM),School of Chemistry,Sun Yat-Sen University,Guangzhou,510275,China

Chen，Xiaodan,Hu，Chenyang,Zhang，Xu,et al. Reversible Stereoisomerization of 1,3-Diphosphetane Frameworks Revealed by a Single-Electron Redox Approach[J]. INORGANIC CHEMISTRY,2021,60(8):5771-5778.

Chen，Xiaodan.,Hu，Chenyang.,Zhang，Xu.,Liu，Shihua.,Mei，Yanbo.,...&Su，Cheng Yong.(2021).Reversible Stereoisomerization of 1,3-Diphosphetane Frameworks Revealed by a Single-Electron Redox Approach.INORGANIC CHEMISTRY,60(8),5771-5778.

Chen，Xiaodan,et al."Reversible Stereoisomerization of 1,3-Diphosphetane Frameworks Revealed by a Single-Electron Redox Approach".INORGANIC CHEMISTRY 60.8(2021):5771-5778.