Synthesis, Structure, and Reactivity of a Stabilized Phosphiranylium Salt

Jansen, Helen; Läng, Florian; Slootweg, J. Chris; Ehlers, Andreas W.; Lutz, Martin; Lammertsma, Koop

doi:10.1002/anie.201000901

Cited by 18 publications

(6 citation statements)

References 52 publications

(20 reference statements)

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“…This bonding formulation has previously been proposed for relatedp hosphorus-containing compounds. [32][33][34] It is interesting to note that while 1a reacts with HOTf to afford ap hosphorus(III) compound with ap rotonated ligand backbone( 6a), the analogous reaction with an acidt hat has am ore nucleophilic counter-anion, such as HCl, affords the phosphorus(V) species HPCl(ONO) (8a). This differencei nr eactivity suggests that mechanistically,asufficientlys trongn ucleophile is required to afford the formal phosphorus(V) oxidative addition product.…”

Section: Reactivity Of 1a and 1b Towardselectrophilesmentioning

confidence: 99%

On the Ambiphilic Reactivity of Geometrically Constrained Phosphorus(III) and Arsenic(III) Compounds: Insights into Their Interaction with Ionic Substrates

Robinson

Rosa

et al. 2016

Chemistry A European J

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The ambiphilic nature of geometrically constrained Group 15 complexes bearing the N,N-bis(3,5-di-tert-butyl-2-phenolate)amide pincer ligand (ONO 3À )i se xplored. Despite their differing reactivity towards nucleophilic substrates with polarised element-hydrogen bonds (e.g.,N H 3 ), both the phosphorus(III), P(ONO)( 1a), anda rsenic(III), As(ONO)( 1b), compounds exhibit similar reactivity towards charged nucleophilesa nd electrophiles. Reactions of 1a and 1b with KOtBu or KNPh 2 afford anionicc omplexes in which the nucleophilic anion associates with the pnictogen centreÀ (Pn = P( 3a), As (3b)).C ompound 2a can subsequentlybe reacted with ap rotons ource or benzylbromide to afford the phosphorus(V) compounds (tBuO)HP(O-NO) (4a)a nd (tBuO)BzP(ONO) (5a), respectively,w hereas analogous arsenic(V) compounds are inaccessible.E lectrophilic substrates, such as HOTf and MeOTf, preferentially associate with the nitrogen atom of the ligand backbone of both 1a and 1b,g iving rise to cationic species that can be rationalised as either ammonium salts or as amine-stabilised phospheniumo ra rsenium complexes( [Pn{ON(H)O}] + (Pn = P (6a), As (6b)) and [Pn{ON(Me)O}] + (Pn = P( 7a), As (7b)). Reactiono f1a with an acid bearing an ucleophilic counteranion (such as HCl) gives rise to ap hosphorus(V) compound HPCl(ONO) (8a), whereas the analogous reaction with 1b results in the addition of HCl across one of the AsÀOb onds to afford ClAs{(H)ONO} (8b). Functionalisation at both the pnictogenc entre and the ligand backbone is also possible by reactiono f7a/7b with KOtBu, which affords the neutral species (tBuO)Pn{ON(Me)O} (Pn = P( 9a), As (9b)).T he ambiphilic reactivity of theseg eometrically constrainedc omplexes allowss omei nsight into the mechanism of reactivity of 1a towardssmall molecules, such as ammonia and water.

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Section: Reactivity Of 1a and 1b Towardselectrophilesmentioning

confidence: 99%

On the Ambiphilic Reactivity of Geometrically Constrained Phosphorus(III) and Arsenic(III) Compounds: Insights into Their Interaction with Ionic Substrates

Robinson

Rosa

et al. 2016

Chemistry A European J

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“…It was obtained by displacement of the intramolecular tertiary amine ligand of the phosphiranylium complex 9 by the independently generated NHC, acting as a stronger donor than the amine (Scheme 5). 29 It is noteworthy that both 9 and 10 can also be described by their amoniophosphine and carbeniophosphine Lewis structures, respectively. DFT studies of 10 confirmed the strong s-donation of the NHC lone pair to the empty p orbital of the phosphenium center, but revealed a small p-back-donation of the phosphenium lone pair competing with the nitrogen lone pairs in their interaction with the empty p z * orbital of the sp 2carbon atom.…”

Section: Imidazoliophosphine Systemsmentioning

confidence: 99%

Carbeniophosphanes and their carbon → phosphorus → metal ternary complexes

et al. 2012

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The discovery, recent developments and prospects of the carbeniophosphines, and in particular of imidazoliophosphines, are related. The P-conjugated positive charge brought by the stabilized carbenium center gives stable (Im + )R 2 Pmetal dative bonds, while the ligands themselves contain a relatively stable C -P + R 2 dative bond, making imidazoliophosphines, more accurately described as NHC-phosphenium adducts. The preparation methods, structural features, electronic and coordination properties, reactivity, and catalytic properties of carbeniophosphines are reviewed.

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“…The Grützmacher group reported the synthesis, structures, and reactivities of very stabilized phosphiranes, and phosphiranium and phosphiranylium salts via an approach of incorporating the PC2 cycle within a polycyclic framework (Figure 28). [199][200][201][202] 5-Dibenzosuberenone (1) was used as a platform for the synthesis of the highly strained dibenzophosphasemibullvalene 356, 199 very robust phosphaazabarbaralanes (BABAR-Phos) as 357, which was named in a manner analogous to the hydrocarbon 360 (barbaralane), 200 the phosphiranium ion 358, 201,202 and phosphiranylium salt 359. 202 The straightforward synthesis of BABAR-Phos 357 is shown in Scheme 59.…”

Section: Scheme 58 Reactions Of Tris(trimethylsilyl)silyllithium Withmentioning

confidence: 99%

“…201 Treatment of the corresponding N-methyl-BABAR-Phos resembling 357 with methyl triflate as a strongly alkylating agent afforded an exclusively N-alkylation product 359. 202 Polycyclic framework BABAR-Phos-type phosphiranes allowed the synthesis of various platinum(0) com-…”

Section: Scheme 58 Reactions Of Tris(trimethylsilyl)silyllithium Withmentioning

confidence: 99%

The Dibenzosuberenone Scaffold as a Privileged Substructure: From Synthesis to Application

2017

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Numerous studies on dibenzosuberenones, especially on 5-dibenzosuberenones, have emerged in recent years. This review focuses on the chemistry of dibenzosuberenones, including their synthesis and applications, which are currently used as tools by the synthetic and biological communities.1 Introduction2 5-Dibenzosuberenone (5H-Dibenzo[a,d]cyclohepten-5-one)2.1 Synthesis of 5-Dibenzosuberenone2.2 Reactions of 5-Dibenzosuberenone3 5H-Dibenzo[a,c]cyclohepten-5-one3.1 Synthesis of 5H-Dibenzo[a,c]cyclohepten-5-one3.2 Reactions of 5H-Dibenzo[a,c]cyclohepten-5-one4 6H-Dibenzo[a,c]cyclohepten-6-one and 10H-Dibenzo[a,d]cyclohepten-10-one4.1 Generation and Trapping of 6H-Dibenzo[a,c]cyclohepten-6-one and 10H-Dibenzo[a,d]cyclohepten-10-one5 Dibenzocycloheptenediones5.1 Synthesis of Dibenzocycloheptenediones5.2 Reactions of Dibenzocycloheptenediones6 Conclusion

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Synthesis, Structure, and Reactivity of a Stabilized Phosphiranylium Salt

Cited by 18 publications

References 52 publications

On the Ambiphilic Reactivity of Geometrically Constrained Phosphorus(III) and Arsenic(III) Compounds: Insights into Their Interaction with Ionic Substrates

On the Ambiphilic Reactivity of Geometrically Constrained Phosphorus(III) and Arsenic(III) Compounds: Insights into Their Interaction with Ionic Substrates

Carbeniophosphanes and their carbon → phosphorus → metal ternary complexes

The Dibenzosuberenone Scaffold as a Privileged Substructure: From Synthesis to Application

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