Reversible Activation and Transfer of White Phosphorus by Silyl‐Stannylene

Sarkar, Debotra; Weetman, Catherine; Munz, Dominik; Inoue, Shigeyoshi

doi:10.1002/ange.202013423

Cited by 17 publications

(2 citation statements)

References 56 publications

(41 reference statements)

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“…A commonly encountered reactivity pattern involves insertion of the main group fragment into one of the P‐P single bonds of the P 4 tetrahedron ( I , Figure 1). Such complexes have been isolated using silylenes, [6] germylenes, [7] stannylenes [8] and in situ generated phosphenium cations [9] . However, P 4 reactivity can often be unpredictable, affording vastly different products depending on the steric and electronic properties of the supporting ligands.…”

Section: Figurementioning

confidence: 99%

“…Reports of the reactivity of main group complexes containing the η 2 ‐P 4 2− ligand remain sparse in the literature, being limited to photolytic P 4 release [7a, 8] and functionalization using Lewis acidic transition metal fragments [7b] . Given the now well‐established reducing nature of aluminyl compounds, [13] we wondered whether the P 4 unit in 2 would undergo further stepwise reduction if an additional equivalent of [(NON)Al] − was added.…”

Section: Figurementioning

confidence: 99%

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Generation of a π‐Bonded Isomer of [P₄]⁴⁻by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH₃

et al. 2021

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By employing the highly reducing aluminyl complex [K{(NON)Al}]2 (NON=4,5‐bis(2,6‐diisopropylanilido)‐2,7‐di‐tert‐butyl‐9,9‐dimethylxanthene), we demonstrate the controlled formation of P42− and P44− complexes from white phosphorus, and chemically reversible inter‐conversion between them. The tetra‐anion features a unique planar π‐bonded structure, with the incorporation of the K+ cations implicit in the use of the anionic nucleophile offering additional stabilization of the unsaturated isomer of the P44−fragment. This complex is extremely reactive, acting as a source of P3−: exposure to ammonia leads to the release of phosphine (PH3) under mild conditions (room temperature and pressure), which contrast with those necessitated for the direct combination of P4 and NH3 (>5 kbar and >250 °C).

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Section: Figurementioning

confidence: 99%

Section: Figurementioning

confidence: 99%

Generation of a π‐Bonded Isomer of [P₄]⁴⁻by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH₃

et al. 2021

View full text Add to dashboard Cite

show abstract

Generation of a π‐Bonded Isomer of [P₄]⁴⁻by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH₃

et al. 2021

View full text Add to dashboard Cite

By employing the highly reducing aluminyl complex [K{(NON)Al}]2(NON=4,5‐bis(2,6‐diisopropylanilido)‐2,7‐di‐tert‐butyl‐9,9‐dimethylxanthene), we demonstrate the controlled formation of P42−and P44−complexes from white phosphorus, and chemically reversible inter‐conversion between them. The tetra‐anion features a unique planar π‐bonded structure, with the incorporation of the K+cations implicit in the use of the anionic nucleophile offering additional stabilization of the unsaturated isomer of the P44−fragment. This complex is extremely reactive, acting as a source of P3−: exposure to ammonia leads to the release of phosphine (PH3) under mild conditions (room temperature and pressure), which contrast with those necessitated for the direct combination of P4and NH3(>5 kbar and >250 °C).

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Recent Breakthroughs in P₄ Chemistry: Towards Practical, Direct Transformations into P₁ Compounds

Scott

2022

Angewandte Chemie

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For several decades, academic researchers have been intensively studying the chemistry of white phosphorus (P 4 ) in the hope of developing direct methods for its transformation into useful P-containing products. This would bypass the hazardous, multistep procedures currently relied on by industry. However, while academically interesting P 4 activation reactions have become well established, their elaboration into useful, general synthetic procedures has remained out of reach. Very recently, however, a series of independent reports has begun to change this state of affairs. Each shows how relatively simple and practical synthetic methods can be used to access academically or industrially relevant P 1 compounds from P 4 directly, in "one pot" or even in a catalytic fashion. These reports mark a step change in the field of P 4 chemistry, and suggest its possible transition from an area of largely academic interest to one with the promise of true synthetic relevance.

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Reversible Activation and Transfer of White Phosphorus by Silyl‐Stannylene

Cited by 17 publications

References 56 publications

Generation of a π‐Bonded Isomer of [P₄]⁴⁻by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH₃

Generation of a π‐Bonded Isomer of [P₄]⁴⁻by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH₃

Generation of a π‐Bonded Isomer of [P₄]⁴⁻by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH₃

Recent Breakthroughs in P₄ Chemistry: Towards Practical, Direct Transformations into P₁ Compounds

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Reversible Activation and Transfer of White Phosphorus by Silyl‐Stannylene

Cited by 17 publications

References 56 publications

Generation of a π‐Bonded Isomer of [P4]4−by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH3

Generation of a π‐Bonded Isomer of [P4]4−by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH3

Generation of a π‐Bonded Isomer of [P4]4−by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH3

Recent Breakthroughs in P4 Chemistry: Towards Practical, Direct Transformations into P1 Compounds

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Generation of a π‐Bonded Isomer of [P₄]⁴⁻by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH₃

Generation of a π‐Bonded Isomer of [P₄]⁴⁻by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH₃

Generation of a π‐Bonded Isomer of [P₄]⁴⁻by Aluminyl Reduction of White Phosphorus and its Ammonolysis to PH₃

Recent Breakthroughs in P₄ Chemistry: Towards Practical, Direct Transformations into P₁ Compounds