Full P4 to P3− Reduction with a Redox-Active Metal Crown Complex

Maurer J, Schmidt M, Nägel M, Färber C, Langer J, Harder S (2025)

Publication Type: Journal article

Publication year: 2025

Journal

DOI: 10.1002/anie.202515157

Abstract

Traditional bulk syntheses of phosphorus compounds start with P4 to PCl3 oxidation but more sustainable methods cleave P─P bonds reductively. This generally results in larger polyphosphide Zintl anions: Pmⁿˉ. We report a relatively selective full reduction of P4 at room temperature to give a unique hydrocarbon-soluble s-block metal complex of the P³ˉ anion. Key to this chemistry is a recently reported redox-active metal crown complex: (BDI*)MgNa3N″2 (VI); N″ = N(SiMe3)2 and BDI* = HC[(tBu)C═N-DIPeP]2, DIPeP = 2,6-CHEt2-phenyl. The reduction of P4 according to 2 VI + 0.25 P4 → (BDI*)MgNa5N″3P (1) + 0.5 [(BDI*)Mg]2 + 0.33 (NaN″)3 is calculated to be exothermic (ΔH = −40.5 kcal mol⁻¹). The crystal structure of 1 shows a strongly bound (BDI*)MgP²ˉ anion with two chelating [Na-N″-Na⁺] and [Na-N″-Na-N″-Na⁺] arms of unequal length. Although these arms are highly fluxional and rapidly exchange ions, they effectively stabilize the P³ˉ anion. DFT calculations confirm the highly ionic nature of the complex and describe P³ˉ as full valence-shell anion with four lone-pairs of electrons. Reactivity studies show that the P³ˉ anion can react as a triple Brønsted base, a three-fold nucleophile or as a reducing agent.

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How to cite

APA:

Maurer, J., Schmidt, M., Nägel, M., Färber, C., Langer, J., & Harder, S. (2025). Full P4 to P3− Reduction with a Redox-Active Metal Crown Complex. Angewandte Chemie International Edition. https://doi.org/10.1002/anie.202515157

MLA:

Maurer, Johannes, et al. "Full P4 to P3− Reduction with a Redox-Active Metal Crown Complex." Angewandte Chemie International Edition (2025).

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