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Study of the Air‐Tolerant 1,3‐Diphosphacyclobutane‐2,4‐diyl through the Direct Arylation
Author(s) -
Ito Shigekazu
Publication year - 2018
Publication title -
the chemical record
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.61
H-Index - 78
eISSN - 1528-0691
pISSN - 1527-8999
DOI - 10.1002/tcr.201700052
Subject(s) - aryne , chemistry , regioselectivity , aryl , nucleophile , chromophore , steric effects , photochemistry , density functional theory , medicinal chemistry , computational chemistry , stereochemistry , organic chemistry , catalysis , alkyl
Installing π‐functional substituents on the skeletal phosphorus atoms of the air‐tolerant 1,3‐diphosphacyclobutane‐2,4‐diyl unit are promising for tuning the open‐shell singlet P‐heterocyclic chromophore. The sterically encumbered 1,3‐diphosphaCycloButen‐4‐yl Anion ( CBA ), generated from the phosphorus‐carbon triple bond, was available for the regioselective arylation via nucleophilic aromatic substitution (S N Ar) reaction, addition to arynes, and single‐electron transfer (SET) process affording the corresponding P‐arylated 1,3‐diphosphacyclobutane‐2,4‐diyls. The photo‐absorption and redox properties correlated with the effects of the aryl substituents on the 1,3‐diphosphacyclobutane‐2,4‐diyl unit. The X‐ray analyses enabled not only to discuss the metric parameters but also to visualize the radicalic electrons via the electron‐density distribution analysis. The electron‐donating character of the P‐heterocyclic chromophores induced the p‐type semiconductor behavior. Detection of hydrogen fluoride via formation of the 1 λ 5 ,3 λ 5 ‐diphosphete derivative was also developed.