Selective heterolytic P–P bond cleavage of white phosphorus by a frustrated carbene-borane Lewis pair

Holschumacher, Dirk; Bannenberg, Thomas; Ibrom, Kerstin; Daniliuc, Constantin G.; Jones, Peter G.; Tamm, Matthias

doi:10.1039/c0dt01045f

Cited by 84 publications

(62 citation statements)

References 51 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Lastly, a frustrated Lewis pair (FLP) approach, based on the use of carbene I t Bu (I t Bu=1,3‐bis( tert ‐butyl)‐imidazol‐2‐ylidene) and B(C 6 F 5 ) 3 , was reported by Tamm et al . The NHC was found to bind “abnormally” (mesoionic) in the reaction with P 4 and induced a heterolytic P−P bond cleavage [Eq.…”

Section: Functionalization Of P4 Using Carbenesmentioning

confidence: 99%

See 1 more Smart Citation

Functionalization of P₄ through Direct P−C Bond Formation

Borger

Ehlers

Slootweg

et al. 2017

Chemistry A European J

View full text Add to dashboard Cite

Research on chlorine‐free conversions of P4 into organophosphorus compounds (OPCs) has a long track record, but methods that allow desirable, direct P−C bond formations have only recently emerged. These include the use of metal organyls, carbenes, carboradicals, and photochemical approaches. The versatile product scope enables the preparation of both industrially relevant organophosphorus compounds, as well as a broad range of intriguing new compound classes. Herein we provide a concise overview of recent breakthroughs and outline the acquired fundamental insights to aid future developments.

show abstract

Section: Functionalization Of P4 Using Carbenesmentioning

confidence: 99%

“…34, Scheme12). [46] Lastly,afrustrated Lewis pair( FLP) approach, based on the use of carbene ItBu (ItBu = 1,3-bis(tert-butyl)-imidazol-2-ylidene) and B(C 6 F 5 ) 3 ,w as reported by Ta mm et al [48] The NHC was Scheme11. Reactivity of P 4 with CAACs.…”

Section: Functionalization Of P 4 Using Carbenesmentioning

confidence: 99%

Functionalization of P₄ through Direct P−C Bond Formation

Borger

Ehlers

Slootweg

et al. 2017

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Das entstandene Addukt entspricht einem Imidazolium-4-ylidenCarben (häufig als "anormales" Carben bezeichnet), dessen Substituenten sowie die des B(C 6 F 5 ) 3 eine trans-trans-Anordnung einnehmen. [87,89] Die Umlagerung der normalen Carbenposition zur "anormalen" ist bei Reaktionen mit FLPNHCs häufig zu beobachten und wird durch eine Dehydrierung des Carben-Rückgrats durch das FLP ausgelçst. Durch FLP-Dehydrierung der Germane 117 stellten Roesky und Mitarbeiter interessante Germylene wie 118 her.…”

Section: Aufsätzeunclassified

Komplexe von N‐heterocyclischen Carbenen mit Boranen: Synthese und Reaktionen

et al. 2011

View full text Add to dashboard Cite

Borane sind weit verbreitete Lewis‐Säuren, und N‐heterocyclische Carbene (NHCs) sind beliebte Lewis‐Basen. Dennoch war bis in die jüngste Zeit erstaunlich wenig über Komplexe dieser beiden Verbindungsklassen miteinander bekannt. NHC‐Borane sind leicht herzustellen, und teilweise sind sie so stabil, dass sie weniger als Komplex, sondern vielmehr als eigenständige organische Verbindung betrachtet werden können. Sie verhalten sich nicht wie klassische Borane, und sie können ein breites Spektrum an funktionellen Gruppen enthalten. Als vielseitige Reaktionspartner, Reagentien und Katalysatoren verfügen NHC‐Borane über ein immenses Potenzial für die organische Synthese und die Polymerchemie. Viele Reaktionen von NHC‐Boranen laufen über neue reaktive Intermediate wie Boreniumkationen, Borylradikale und sogar Borylanionen ab. Hier geben wir eine umfassende Übersicht über die Synthese, Charakterisierung und Reaktionen von NHC‐Boranen.

show abstract

“…[31,[41][42][43] Indeed, the chemistry of Group 12 metal-aNHC complexes is unexplored. [27,28,36] We synthesized the first aNHC-zinc complex 5 (Scheme 2) by reaction of 1:3 triorganozincate 2 with excess MeOTf.…”

mentioning

confidence: 99%

NHC‐Stabilized Triorganozincates: Syntheses, Structures, and Transformation to Abnormal Carbene–Zinc Complexes

et al. 2012

View full text Add to dashboard Cite

The chemistry of organozinc compounds has been inextricably entwined with the development of organic synthetic methods since Franklands seminal discovery of zinc alkyls in 1849. [1,2] Compared to diorganozinc reagents, the corresponding anionic zincate derivatives are considerably better nucleophiles. [3][4][5][6][7][8] Consequently, triorganozincates [R 3 Zn]M (M = alkali metals) and tetraorganozincates [R 4 Zn]M n (M = alkali metals, n = 2; M = alkali earth metals, n = 1) have been extensively utilized in organic transformations such as halogen-metal exchanges, [9][10][11][12] nucleophilic additions, [1,2] deprotonative metalations, [6][7][8] and epoxide ring-openings. [9,10] Recently, Mulvey et al. employed TMP-zincates (TMP = 2,2,6,6-tetramethylpiperidide) in developing a zincationanion trapping strategy [13] and in realizing the unusual transformation of a diamine into an unsaturated diazaethene through a lithium/zinc bimetallic system. [14,15] The advantages of organozincates may be attributed to their intrinsic "bimetallic" character. Indeed, due to their synergic reactivity, bimetallic systems often outperform their monometallic components and have shown greater potential in organic transformations. [6] Lithium zincate investigations reveal that not only the Li/Zn ratio [3,4,9] but also the substituents [5] may have remarkable effects on their reactivity. Thus, the TMP ligand has contributed to the renaissance of metallation chemistry involving organozincate compounds. [6][7][8] We show here that extensions of the ligand systems can result in organozincates with novel reactivity.While N-heterocyclic carbenes (NHCs) have become ubiquitous ligands for organic [16] and transition-metal [16] catalysis, they are also capable of stabilizing highly reactive main group molecules. [17][18][19][20][21][22] NHC-zinc complexes may act as polymerization catalysts. [23][24][25][26] However, all the reported NHC-based zinc compounds are neutral and C2-bound. Considering the unique application of C4-bound NHC [i.e., Scheme 1. Synthesis of NHC-stabilized triorganozincates 2 and 3.

show abstract

Selective heterolytic P–P bond cleavage of white phosphorus by a frustrated carbene-borane Lewis pair

Cited by 84 publications

References 51 publications

Functionalization of P₄ through Direct P−C Bond Formation

Functionalization of P₄ through Direct P−C Bond Formation

Komplexe von N‐heterocyclischen Carbenen mit Boranen: Synthese und Reaktionen

NHC‐Stabilized Triorganozincates: Syntheses, Structures, and Transformation to Abnormal Carbene–Zinc Complexes

Contact Info

Product

Resources

About

Selective heterolytic P–P bond cleavage of white phosphorus by a frustrated carbene-borane Lewis pair

Cited by 84 publications

References 51 publications

Functionalization of P4 through Direct P−C Bond Formation

Functionalization of P4 through Direct P−C Bond Formation

Komplexe von N‐heterocyclischen Carbenen mit Boranen: Synthese und Reaktionen

NHC‐Stabilized Triorganozincates: Syntheses, Structures, and Transformation to Abnormal Carbene–Zinc Complexes

Contact Info

Product

Resources

About

Functionalization of P₄ through Direct P−C Bond Formation

Functionalization of P₄ through Direct P−C Bond Formation