67 / 2023-08-16 15:05:14

Electrochemical activation of P4 for the synthesis of organophosphorus compounds and complex structures

P4 activation; Electrochemistry; Dicyanophosphide; 2-Center-3-electron π-bond

New Technologies in Phosphorus Chemistry > 1) New reagents and methods in organophosphorus Chemistry

Organophosphorus compounds (OPCs) have wide applications ranging from synthetic chemistry to materials and biological sciences. The synthetic methods of most OPCs mainly rely on toxic and corrosive PCl₃ and PH₃ as phosphorus transfer reagents. We describe herein a practical and versatile approach for the transformation of white phosphorus (P₄) into useful OPCs with high P atom economy via a key bridging anion dicyanophosphide [P(CN)₂]⁻. This anion can be directly prepared on a gram scale from P₄ through an electrochemical process using simple starting materials. A variety of valuable OPCs involving phosphinidenes, cyclophosphanes, and phospholides have been made readily accessible from P₄ in a two-step manner.

Other unprecedented complex structures with unique electronic properties can also be achieved from [P(CN)₂]⁻. We demonstrate the synthesis of radical anion featuring a 2-center-3-electron π-bond based on phosphorus atoms. In addition, CAAC stabilized tri-phosphorus anion [P₃]⁻, the heavier analogue of azide anion, and its derivatives were obtained from [P(CN)₂]⁻.