Formation of a P162- Ink from Elemental Red Phosphorus in a Thiol-Amine Mixture

Marissa J Strumolo; Dmitry B Eremin; Shuai Wang; Carlos Mora Perez; Oleg V Prezhdo; Joshua S Figueroa; Richard L Brutchey

doi:10.1021/acs.inorgchem.3c00370

Formation of a P₁₆^2- Ink from Elemental Red Phosphorus in a Thiol-Amine Mixture

Inorg Chem. 2023 Apr 24;62(16):6197-6201. doi: 10.1021/acs.inorgchem.3c00370. Epub 2023 Apr 11.

Authors

Marissa J Strumolo¹, Dmitry B Eremin^{1

2}, Shuai Wang³, Carlos Mora Perez¹, Oleg V Prezhdo¹, Joshua S Figueroa³, Richard L Brutchey¹

Affiliations

¹ Department of Chemistry, University of Southern California, Los Angeles, California 90089, United States.
² The Bridge@USC, University of Southern California, Los Angeles, California 90089, United States.
³ Department of Chemistry and Biochemistry, University of California─San Diego, La Jolla, California 92093, United States.

Abstract

A P₁₆^2- polyphosphide dianion ink was produced by the reaction of red phosphorus with a binary thiol-amine mixture of ethanethiol (ET) and ethylenediamine (en). The polyphosphide was identified by solution ³¹P NMR spectroscopy and electrospray ionization mass spectrometry. This solute was compared to the reaction products of white phosphorus (P₄) and other elemental pnictides in the same solvent system. The reaction of P₄ with ET and en gives the same P₁₆^2- polyphosphide; however, the easier handling and lower reactivity of red phosphorus highlights the novelty of that reaction. Elemental arsenic and antimony both give mononuclear pnictogen-sulfide-thiolate complexes upon reaction with ET and en under otherwise identical conditions, with this difference likely resulting from the greater covalency and tendency of phosphorus to form P-P bonds.