The Reaction of Chloramine with Some Trisubstituted Phosphines<sup>1</sup>

Sisler, Harry H.; Sarkis, Adib Jabbur; Ahuja, H. S.; Drago, R.J.; Smith, Nathan L.

doi:10.1021/ja01521a016

Cited by 37 publications

(12 citation statements)

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“…Examples of aminophosphonium cations, [R 3 P‐NR′ 2 ][X], have been known since the 1950s and can be accessed by various routes, including salt metathesis and quaternization of aminophosphines 44–48. They are also, however, formed in the reaction of phosphines with haloamines (Scheme ),36, 47–53 as exemplified by the reaction of Ph 3 P with NH 2 Cl in Et 2 O solution to quantitatively yield [Ph 3 P‐NH 2 ][Cl]. These reactions are again perceived to occur by an S N 2‐type reaction of the phosphine donor with an electrophilic nitrogen acceptor.…”

Section: Cationic Complexes Of Nitrogen Acceptorsmentioning

confidence: 99%

Interpnictogen Cations: Exploring New Vistas in Coordination Chemistry

2014

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Pnictine derivatives can behave as both 2e(-) donors (Lewis bases) and 2e(-) acceptors (Lewis acids). As prototypical ligands in the coordination chemistry of transition metals, amines and phosphines also form complexes with p-block Lewis acids, including a variety of pnictogen-centered acceptors. The inherent Lewis acidity of pnictogen centers can be enhanced by the introduction of a cationic charge, and this feature has been exploited in recent years in the development of compounds resulting from coordinate Pn-Pn and Pn-Pn' interactions. These compounds offer the unusual opportunity for homoatomic coordinate bonding and the development of complexes that possess a lone pair of electrons at the acceptor center. This Review presents new directions in the systematic extension of coordination chemistry from the transition series into the p-block.

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Section: Cationic Complexes Of Nitrogen Acceptorsmentioning

confidence: 99%

Interpnictogen Cations: Exploring New Vistas in Coordination Chemistry

2014

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“…[44][45][46][47][48] Doch sie werden auch in der Reaktion von Phosphanen mit Halogenaminen gebildet (Schema 6), [36,[47][48][49][50][51][52][53] [51] Relativ kurze N-P-Bindungen (ca. [44][45][46][47][48] Doch sie werden auch in der Reaktion von Phosphanen mit Halogenaminen gebildet (Schema 6), [36,[47][48][49][50][51][52][53] [51] Relativ kurze N-P-Bindungen (ca.…”

Section: Phosphordonoren An Stickstoffakzeptorenunclassified

“…Aminophosphoniumkationen, [R 3 P-NR' 2 ][X], sind seit den 1950er Jahren bekannt und kçnnen auf verschiedenen Wegen synthetisiert werden, einschließlich Salzmetathese und Quaternisierung von Aminophosphanen. [44][45][46][47][48] Doch sie werden auch in der Reaktion von Phosphanen mit Halogenaminen gebildet (Schema 6), [36,[47][48][49][50][51][52][53] [51] Relativ kurze N-P-Bindungen (ca. 1.63 , [46,[54][55][56][57][58] S CR = 1.80 ) und die Planarität des Stickstoffzentrums in den meisten Aminophosphoniumkationen legen einen gewissen N-P-Mehrfachbindungscharakter nahe (siehe Abbildung 3), der mit der Wechselwirkung des freien Elektronenpaars am Stickstoff mit s*-Orbitalen am Phosphor erklärt wird.…”

Section: Phosphordonoren An Stickstoffakzeptorenunclassified

Interpniktogenkationen: Neue Perspektiven in der Koordinationschemie

2014

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Pniktanderivate können die Rolle von sowohl 2 e−‐Donoren (Lewis‐Basen) als auch 2 e−‐Akzeptoren (Lewis‐Säuren) übernehmen. Als prototypische Liganden in der Koordinationschemie von Übergangsmetallen bilden Amine und Phosphane auch Komplexe mit Lewis‐Säuren des p‐Blocks, die verschiedene Pniktogen‐zentrierte Akzeptoren umfassen. Die Lewis‐Acidität von Pniktogenzentren kann durch eine kationische Ladung verstärkt werden, was in den letzten Jahren zur Entwicklung von Verbindungen mit koordinativen Pn‐Pn‐ und Pn‐Pn′‐Wechselwirkungen genutzt wurde. Diese Verbindungen bieten die außergewöhnliche Möglichkeit zur homoatomaren Koordinationsbindung und ermöglichen die Entwicklung von Komplexen mit einem freien Elektronenpaar am Akzeptorzentrum. Dieser Aufsatz weist neue Richtungen für die systematische Erweiterung der Koordinationschemie von der Übergangsreihe zum p‐Block.

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“…succeeded in the isolation of the first iminophosphorane Ph 3 P=NH ( 2 a ) by the deprotonation of the corresponding iminium halide with sodium amide in liquid ammonia [27,28] . Iminophosphoranes 2 of the general formula R 3 P=NH are accessible by the reaction of phosphines with chloramines [28,29] . Another convenient method for the synthesis of 2 was developed by Birkofer in 1964 through Staudinger reactions of phosphines with trimethylsilylazide and the subsequent acid catalyzed hydrolysis of initially obtained trimethylsilyl iminophosphoranes 3 in methanol (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

“…The syntheses of the mono‐ to tris(dimethylamino) derivatives were performed according to the procedure by Appel et al. (Schemes 1 and 2) through the reaction of phosphines with chloramines and subsequent deprotonation [27–29] . This series was completed by Goubeau et al.…”

Section: Introductionmentioning

confidence: 99%

Phosphorus‐Containing Superbases: Recent Progress in the Chemistry of Electron‐Abundant Phosphines and Phosphazenes

Weitkamp

Neumann

Stammler

et al. 2021

Chemistry A European J

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The renaissance of Brønsted superbases is primarily based on their pronounced capacity for a large variety of chemical transformations under mild reaction conditions. Four major set screws are available for the selective tuning of the basicity: the nature of the basic center (N, P, …), the degree of electron donation by substituents to the central atom, the possibility of charge delocalization, and the energy gain by hydrogen bonding. Within the past decades, a plethora of neutral electron-rich phosphine and phosphazene bases have appeared in the literature. Their outstanding properties and advantages over inorganic or charged bases have now made them indispensable as auxiliary bases in deprotonation processes. Herein, an update of the chemistry of basic phosphines and phosphazenes is given. In addition, due to widespread interest, their use in catalysis or as ligands in coordination chemistry is highlighted.

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The Reaction of Chloramine with Some Trisubstituted Phosphines¹

Cited by 37 publications

References 0 publications

Interpnictogen Cations: Exploring New Vistas in Coordination Chemistry

Interpnictogen Cations: Exploring New Vistas in Coordination Chemistry

Interpniktogenkationen: Neue Perspektiven in der Koordinationschemie

Phosphorus‐Containing Superbases: Recent Progress in the Chemistry of Electron‐Abundant Phosphines and Phosphazenes

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The Reaction of Chloramine with Some Trisubstituted Phosphines1

Cited by 37 publications

References 0 publications

Interpnictogen Cations: Exploring New Vistas in Coordination Chemistry

Interpnictogen Cations: Exploring New Vistas in Coordination Chemistry

Interpniktogenkationen: Neue Perspektiven in der Koordinationschemie

Phosphorus‐Containing Superbases: Recent Progress in the Chemistry of Electron‐Abundant Phosphines and Phosphazenes

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The Reaction of Chloramine with Some Trisubstituted Phosphines¹