Thermoneutral N−H Bond Activation of Ammonia by a Geometrically Constrained Phosphine

Abbenseth, Josh; Townrow, Oliver P. E.; Goicoechea, José M.

doi:10.1002/ange.202111017

Cited by 7 publications

(9 citation statements)

References 69 publications

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“…The application of P III species in unusual non‐trigonal coordination environments in NH 3 activation has since attracted considerable interest, [9] and was recently reviewed [10] . Moreover, reversible NH 3 ‐activation using NNS‐type ligands on P III was reported in 2021 (Scheme 1, middle right) [11] . In this regard the reversible H 2 activation and NH 3 activation to give azadiphosphiridines by the neutral biradicaloid [P(μ‐N Mes Ter)] 2 ( Mes Ter=2,6‐(2,4,6‐Me 3 ‐C 6 H 2 ) 2 C 6 H 3 ) is noteworthy [12] .…”

Section: Methodsmentioning

confidence: 99%

“…Then we investigated whether piperidine or HNEt 2 could be NH‐activated, as secondary amine activation was previously only reported for NNS‐substituted P III system in dipolar fashion [11] . RP(PMe 3 ) reacted cleanly with piperidine in C 6 H 6 under sonication for 4 h at elevated temperatures, to give RP(H)N(C 5 H 10 ) ( 6:R , R=Mes*, Mes Ter, Dip Ter) quantitatively as colorless solids.…”

Section: Methodsmentioning

confidence: 99%

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Metal‐Free N−H Bond Activation by Phospha‐Wittig Reagents**

et al. 2022

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N-containing molecules are mostly derived from ammonia (NH 3 ). Ammonia activation has been demonstrated for single transition metal centers as well as for low-valent main group species. Phosphinidenes, mono-valent phosphorus species, can be stabilized by phosphines, giving so-called phosphanylidenephosphoranes of the type RP(PR' 3 ). We demonstrate the facile, metal-free NH 3 activation using ArP(PMe 3 ), affording for the first time isolable secondary aminophosphines ArP(H)NH 2 . DFT studies reveal that two molecules of NH 3 act in concert to facilitate an NH 3 for PMe 3 exchange. Furthermore, H 2 NR and HNR 2 activation is demonstrated.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Metal‐Free N−H Bond Activation by Phospha‐Wittig Reagents**

et al. 2022

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“…Die Anwendung von P III ‐Spezies in ungewöhnlichen nicht‐trigonalen Koordinationsumgebungen bei der NH 3 ‐Aktivierung hat seither erhebliches Interesse geweckt [9, 10] . Darüber hinaus wurde 2021 über eine reversible NH 3 ‐Aktivierung an einer P III ‐Spezies mit einem NNS‐Liganden berichtet (Schema 1, Mitte rechts) [11] . In diesem Zusammenhang ist die reversible H 2 ‐Aktivierung und NH 3 ‐Aktivierung zu Azadiphosphiridinen durch das neutrale Biradikaloid [P(μ‐N Mes Ter)] 2 bemerkenswert ( Mes Ter=2,6‐(2,4,6‐Me 3 ‐C 6 H 2 ) 2 C 6 H 3 ) [12] .…”

Section: Methodsunclassified

“…Anschließend untersuchten wir, ob Piperidin oder HNEt 2 NH‐aktiviert werden können, da die Aktivierung sekundärer Amine bisher nur für NNS‐substituierte P III ‐Systeme in dipolarer Weise beschrieben wurde [11] . RP(PMe 3 ) reagierte mit Piperidin in C 6 H 6 im Ultraschallbad für 4 h bei erhöhten Temperaturen, um RP(H)N(C 5 H 10 ) ( 6:R , R=Mes*, Mes Ter, Dip Ter) quantitativ als farblose Feststoffe zu erhalten.…”

Section: Methodsunclassified

Metallfreie N−H‐Bindungsaktivierung mit Phospha‐Wittig Reagenzien**

et al. 2022

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N-haltige Moleküle werden meist ausgehend von Ammoniak (NH 3 ) dargestellt. Die Ammoniakaktivierung wurde sowohl für individuelle Übergangsmetallzentren als auch für niedervalente Hauptgruppenspezies gezeigt. Phosphinidene, einfach koordinierte Phosphorspezies, können durch Phosphine, in sogenannten Phosphanylidenphosphoranen vom Typ RP(PR' 3 ), stabilisiert werden. Wir demonstrieren hier die einfache, metallfreie NH 3 -Aktivierung mit ArP(PMe 3 ), wodurch zum ersten Mal isolierbare sekundäre Aminophosphine des Typs ArP(H)NH 2 entstehen. DFT-Studien zeigen, dass zwei NH 3 -Moleküle zusammenwirken, um einen Austausch von PMe 3 gegen NH 3 zu ermöglichen. Außerdem wurde die Aktivierung von H 2 NR und HNR 2 nachgewiesen.

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“…The distinctive reactivities exhibited by these derivatives support their inherent potential for development toward effective mediators in other chemical transformations involving different nucleophiles that could be used to access otherwise arduous organic target species. 6,36,42,45,46,50…”

Section: Altering the σ*−π* Interaction Through Hypervalencymentioning

confidence: 99%

Unique Phosphorus-Based Avenues for the Tuning of Functional Materials

2023

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Metrics & MoreArticle Recommendations CONSPECTUS: Recent ground-breaking advances in synthetic chemistry have transformed main-group molecules from simple laboratory curiosities into powerful materials for a range of applications in all realms of life. Electron-accepting or -deficient materials, in particular, have been the focus of development since their generally limited availability and stability have been major hurdles in establishing new practical applications. In addition to the general requirements for the design of these materials, a deeper understanding of their inherent electronics and molecular interactions is a requirement for the successful expansion of their utility. Previously, the incorporation of electron-deficient main-group elements, such as boron, into a conjugated organic framework was considered to be an effective route toward the synthesis of high-performing electron-accepting materials. However, challenging conditions such as the need for bulky substituents for kinetic stabilization, air-free and moisture-sensitive synthesis, and restricted storage abilities have led to the investigation of other elements across the periodic table to be used in a similar vein. Lately, heavier main-group elements such as Si, Ge, P, As, Sb, Bi, S, Se, and Te have also proven to be advantageous for electron-accepting materials as they exhibit polarizable molecular orbitals that are easily accessible to electrons or nucleophiles. This has laid the foundation for materials chemistry research on a variety of applications, including optoelectronic devices such as OLEDs, organic photovoltaics, energy storage such as in batteries and capacitors, fluorescent sensors with both biological and physiological applications, organocatalysis and synthesis, and many more. Among the main-group-element-based materials, organophosphorus species are privileged as their frontier orbitals are easily altered by chemical modification or/and structural and geometrical manipulations at the phosphorus center itself, without the need for kinetic stabilization, or through electronic modification of the conjugated system. The five-membered phosphorus-based heterocycle, phosphole, is a particularly interesting motif in this context, and extensive studies on the corresponding materials have uncovered the rich fundamentals of the σ*−π* interaction that imparts intriguing accepting properties while sustaining morphological and physiological stability for utilization in real-life scenarios. Moreover, beyond the σ*−π* interaction in phospholes that is key to many of their acceptor properties as a material, the use of phosphorus also gives rise to easily accessible, low-lying antibonding orbitals. They pave the way for Lewis acid phosphorus species that, despite being considered to be electron-rich species in general, open up several possibilities for intriguing chemical reactivity through hypervalency. Herein, we representatively discuss some recent advancements through the various approaches that leverage the unique structures and electronics...

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Thermoneutral N−H Bond Activation of Ammonia by a Geometrically Constrained Phosphine

Cited by 7 publications

References 69 publications

Metal‐Free N−H Bond Activation by Phospha‐Wittig Reagents**

Metal‐Free N−H Bond Activation by Phospha‐Wittig Reagents**

Metallfreie N−H‐Bindungsaktivierung mit Phospha‐Wittig Reagenzien**

Unique Phosphorus-Based Avenues for the Tuning of Functional Materials

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