Facile Conversion of Red Phosphorus into Soluble Polyphosphide Anions by Reaction with Potassium Ethoxide

Abstract

Soluble polyphosphide anions were successfully generated in a number of organic solvents by the reaction between shelf-stable red phosphorus and potassium ethoxide. The species were identified by (31)P NMR spectroscopy in solution and by X-ray crystal-structure determination of (Bu4N)2P16 in the solid state. The reaction was scaled up to gram quantities by using a flow-chemistry process.

Mild‐Temperature Solution‐Assisted Encapsulation of Phosphorus into ZIF‐8 Derived Porous Carbon as Lithium‐Ion Battery Anode

“…In order to feasibly encapsulate RP into nanopores of ZIF‐8‐C hosts, the nucleophile sodium ethoxide (NaOEt) was used to activate the decomposition of RP into PP (mainly including ring‐shaped P 5 − anions as well as chain‐shaped P 16 2− and P 21 3− anions) in solution under argon protection. [ 20,30 ] These soluble PP could readily diffuse into the pores of ZIF‐8‐C hosts through capillary phenomenon with the help of ultrasonic forces. In comparison to the conventional high‐temperature evaporation/condensation method, the whole RP encapsulation process was conducted under a mild temperature (i.e., 80 °C), avoiding the conversion of RP to white phosphorus.…”

Black phosphorus synthesized by solvothermal reaction from red phosphorus and its catalytic activity for water splitting

“…Dragulescu-Andrasi et al have shown that potassium ethoxide can convert to soluble polyphosphide from RP. 13 Zhao et al have produced agglomerates of very small BP nanosheet which have a wider band gap than RP by hydrothermal synthesis using ammonium fluoride aqueous solution and RP as reactants. 14 Liu et al reported that synthesis of composite of BP/RP with high photocatalytic activity for water splitting from RP in amine solvent.…”

Peculiar All‐Metal σ‐Aromaticity of the [Au2Sb16]4− Anion in the Solid State

“…Essentially, 1 may be viewed as two Sb 7 units coupled by a Sb 2 dumbbell and pulled together because of the interaction with two Au atoms. From a structural point of view, the Sb 16 cluster can be obtained through structural transformation from the P 16 2− ‐like geometry via bond cleavage and rotation (Figure S3). Noteworthy, such transformation is feasible due to the interaction of each Au atom with four neighboring Sb atoms constituting a somewhat distorted square.…”

“…TheS b-Sb short distances range from 2.72 to 2.85 ,w hich suggests presence of both normal single bonds (2.78-2.86 ) and somewhat shorter single bonds according to Pyykkç. [17] Essentially, 1 may be viewed as two Sb 7 units coupled by aSb 2 dumbbell and pulled together because of the interaction with two Au atoms.From astructural point of view,the Sb 16 cluster can be obtained through structural transformation from the P 16 2À -like geometry [18] via bond cleavage and rotation (Figure S3). Noteworthy,s uch transformation is feasible due to the interaction of each Au atom with four neighboring Sb atoms constituting asomewhat distorted square.Interestingly, the [Au 2 Sb 16 ] 4À cluster (as aseparate gas-phase molecule) was computationally found to be atrue minimum on the potential energy surface (at the PBE0/Def2-TZVPD level of theory) with all bond lengths and angles being pretty close to the experimentally observed values (Table S2).…”