Isolation and Characterization of Radical Anions Derived from a Boryl‐Substituted Diphosphene

Abstract

Radical anions of a diphosphene with two boryl substituents were isolated and characterized by single-crystal X-ray diffraction, electron spin resonance (ESR), and UV/Vis absorption spectroscopy as well as DFT calculations. Structural analysis of the radical anions revealed an elongation of the P=P bond and a contraction of the B-P bonds relative to the neutral diphosphene. The UV/Vis spectra of these radical anions showed a strong absorption in the visible region, which was assigned to SOMO-related transitions on the basis of DFT calculations. The ESR spectra revealed that the hyperfine coupling constant with the phosphorus nuclei is the smallest that has been reported thus far. The results of the DFT calculations furthermore suggest that this should be attributed to a soaking of electron spin to the vacant p orbitals of the boryl substituents.

From stable Sb- and Bi-centered radicals to a compound with a Ga=Sb double bond

“…In contrast to well established P-centered radicals 12–23 , only a few Sb and Bi-centered radicals were reported (Fig. 1) 24 .…”

A Main‐Group Element Radical Based One‐Dimensional Magnetic Chain

“…Thepolymers (1K) n and (1K 2 ) n dissociate into the corresponding monomers in THF solutions as shown by UV/Vis spectroscopy (Supporting Information, Figures S16 and S17). [14] This work demonstrates the potential of self-assembly approach in obtaining main-group element radical based polymers.S ynthesis of more radical polymers with this method and investigation of their physical properties are undergoing in our laboratory.…”

A Tale of Two Elements: The Lewis Acidity/Basicity Umpolung of Boron and Phosphorus

“…have reported the synthesis of a boryl‐phosphine via reactions of the boryl lithium species with chlorophosphines,(see 13 , Scheme ) while Yamashita et al. described the synthesis of a diboryldiphosphene 14 , and most recently, the generation of the corresponding P‐based radicals …”

“…Anionic N-heterocyclic boryl ligands have also been shown to stabilize Al, [19] radicals of Ga and Tl [20] and to provide access to Tl 8 clusters.A ldridge and co-workers [21] have reported the synthesis of boryl derivatives of Si, Ge,Sn, and Pb,including boryl-silylene,and diboryl-tin and lead species,w herein the boryl-silylene was shown to react with H 2 .G udat et al [22] have reported the synthesis of ab oryl-phosphine via reactions of the boryl lithium species with chlorophosphines,(see 13,S cheme 3) while Yamashita et al described the synthesis of ad iboryldiphosphene 14, [23] and most recently,t he generation of the corresponding Pbased radicals. [24]…”