Photoswitchable electron-rich phosphines: using light to modulate the electron-donating ability of phosphines

Abstract

The synthesis and properties of photoswitchable electron-rich phosphines containing N-heterocyclic imines equipped with a photochromic dithienylethene unit are reported.

Synthesis of Halogenated Dibenzo[1,2,6]triazonines and Late-Stage Functionalization of the Triazonine Ring

“…The synthesis of triazonine 8 demonstrates the possibility to introduce phosphine oxide functions on triazonine scaffolds, which expands the still restricted series of photoswitchable phosphorus derivatives , and complements our previous design of azobenzene-based phosphines for catalytic purposes . The phosphine oxide 8 is a C 2 -symmetric compound in which the Ph 2 PO functions are separated from the triazonine ring by a phenyl spacer.…”

Characterization of the Ligand Properties of Donor‐stabilized Pnictogenyltrielanes

“…These compounds have shown remarkable reactivity and basicity while still being easy to access in larger quantities. Typically, these superbasic phosphines are used as ligands in catalysis including reactions such as hydroaminations, coupling reactions, decarbonylations, and many more [14,27] . As shown by Dielmann and co‐workers, however, by the splitting of CO 2 , the superbasic phosphines are powerful enough to activate small molecules [19] …”

Amplified photomodulation of a bis(dithienylethene)-substituted phosphine

“…Dithienylethene–phosphine tethers have been proposed for the light-control of coordination compounds and catalytic reactions, as the electronic changes occurring upon DTE photoisomerization can modulate the electron-donating ability of ligands. 5,21 To our knowledge, this goal has only been explored by attaching one DTE unit to phosphines, either through the central 22 or the lateral thiophene 23–26 rings of the photochromic moiety. Consequently, only limited photomodulation of phosphine properties can be accomplished in this way.…”