Facile Synthesis of the Dicyanophosphide Anion via Electrochemical Activation of White Phosphorus: An Avenue to Organophosphorus Compounds

Organophosphorus compounds (OPCs) have gained tremendous interest in the past decades due to their wide applications ranging from synthetic chemistry to materials and biological sciences. 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 [P(CN)2]–. This anion can be prepared on a gram scale directly from P4 through an unprecedented electrochemical process. A variety of OPCs involving phosphinidenes, cyclophosphanes and phospholides have been made readily accessible from P4 in a two-step manner. Our approach has a significant impact on the future preparation of OPCs in laboratory and industrial settings.

Efficient Electrosynthesis of White Phosphorus from Molten Condensed Phosphate Salts

Elemental white phosphorus (P4) is a crucial feedstock for the entire phosphorus-derived chemicals industry, spanning everything from herbicides to food additives. Currently, industrial P4 production is gated by the infrastructurally demanding reduction of phosphate rock by carbon coke in an arc furnace at temperatures of up to 1500 °C. The electrochemical reduction of phosphate salts could enable the sustainable, point-of-use manufacture of white phosphorus; however, such P4 electrosynthesis requires the rapid activation of strong P—O bonds. Herein, we show that the intrinsic oxide-accepting character of phosphoryl anhydride linkages in molten condensed phosphate salts promotes the reduction of phosphate to white phosphorus at high electron and energy efficiencies. These findings could enable an efficient, low-carbon alternative to legacy carbothermal synthesis of P4.

Chemoselective Facile Synthesis of the Dicyanophosphide Anion via Electrochemical Activation of White Phosphorus: An Avenue to Organophosphorus Compounds

Organophosphorus compounds (OPCs) have gained tremendous interest in the past decades due to their wide applications ranging from synthetic chemistry to materials and biological sciences. We describe herein a practical and versatile approach for the transformation of P4 into useful OPCs with high P atom economy via a key bridging anion [P(CN)2]–. This anion can be prepared on a gram scale directly from P4 through an unprecedented electrochemical process. A variety of OPCs involving phosphinidenes, cyclophosphanes and phospholides have been made readily accessible from P4 in a two-step manner. Our approach has a significant impact on the future preparation of OPCs in laboratory and industrial settings.

Pentaphosphaferrocene-mediated synthesis of asymmetric organo-phosphines starting from white phosphorus

The synthesis of phosphines is based on white phosphorus, which is usually converted to PCl3, to be afterwards substituted step by step in a non-atomic efficient manner. Herein, we describe an alternative efficient transition metal-mediated process to form asymmetrically substituted phosphines directly from white phosphorus (P4). Thereby, P4 is converted to [Cp*Fe(η5-P5)] (1) (Cp* = η5-C5(CH3)5) in which one of the phosphorus atoms is selectively functionalized to the 1,1-diorgano-substituted complex [Cp*Fe(η4-P5R′R″)] (3). In a subsequent step, the phosphine PR′R″R‴ (R′ ≠ R″ ≠ R‴ = alky, aryl) (4) is released by reacting it with a nucleophile R‴M (M = alkali metal) as racemates. The starting material 1 can be regenerated with P4 and can be reused in multiple reaction cycles without isolation of the intermediates, and only the phosphine is distilled off.