On the Versatile and Unusual Coordination Behavior of Ambiphilic Ligands o-R2P(Ph)BR‘2

Bontemps, Sébastien; Bouhadir, Ghenwa; Miqueu, Karinne; Bourissou, Didier

doi:10.1021/ja0637494

Cited by 244 publications

(124 citation statements)

References 16 publications

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“…B. die Produkte 127 und 128 aus solchen Additionsreaktionen mit dem P-B-System 126 erhalten (Schema 47). [81,82] Oft ist es wegen der Empfindlichkeit der metallhaltigen Verbindungen schwierig, an metallorganischen Gerüsten Umwandlungen typischer organischer funktioneller Gruppen durchzuführen. Dies gilt besonders für viele metallorganische Verbindungen "früher" Übergangsmetalle, bei denen erst in jüngster Zeit eine größere Zahl geeigneter Verfahren für solche Transformationen beschrieben wurde.…”

Section: Hydrierungen Unter Verwendung Von Amminboranunclassified

Frustrierte Lewis‐Paare: metallfreie Wasserstoffaktivierung und mehr

2009

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Die Kombination sterisch gehinderter Lewis‐Säuren und ‐Basen führt nicht zur üblichen Neutralisationsreaktion unter Bildung der “klassischen” Lewis‐Säure/Base‐Addukte. Stattdessen stehen die Lewis‐Acidität und ‐Basizität solcher “frustrierten Lewis‐Paare” (FLPs) gemeinsam für die Durchführung ungewöhnlicher Reaktionen zur Verfügung. Typische Beispiele für FLPs bestehen aus inter‐ und intramolekularen Kombinationen sperriger Phosphine und Amine mit stark elektrophilen RB(C6F5)2‐Komponenten. Viele frustrierte Lewis‐Paare sind in der Lage, Wasserstoff heterolytisch zu spalten. Die resultierenden H+/H−‐Paare (z. B. stabilisiert in Form der entsprechenden Phosphonium‐Kation/Hydridoborat‐Anion‐Salze) fungieren als metallfreie Katalysatoren für die Hydrierung sperriger Imine, Enamine, Enolether usw. FLPs reagieren auch mit Alkenen, Carbonylverbindungen und einer Vielzahl anderer kleiner Moleküle, darunter auch Kohlendioxid, in vermutlich kooperativen Dreikomponentenreaktionen. Auf dieser Beobachtung lassen sich neue Synthesestrategien aufbauen.

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Section: Hydrierungen Unter Verwendung Von Amminboranunclassified

Frustrierte Lewis‐Paare: metallfreie Wasserstoffaktivierung und mehr

2009

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“…Further heating leads to completion of the 1,1-carboboration reaction with formation of the internal frustrated Lewis pair E-16. It has previously been shown that related syn-1-boryl-2-phosphanyl alkenes [32] or arenes [33] may serve as bifunctional donor/acceptor ligands in transition metal coordination chemistry and form the respective five-membered chelate metal complexes or related coordination systems (Fig. 5).…”

Section: Resultsmentioning

confidence: 99%

Facile 1,1-Carboboration Reaction of a Diarylphosphino-substituted Conjugated Diyne with Tris(pentafluorophenyl)borane

Feldhaus

Kehr

Fröhlich

et al. 2013

Zeitschrift Für Naturforschung B

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Bis(dimesitylphosphanyl)butadiyne (14) reacts with B(C 6 F 5 ) 3 by a 1,1-carboboration sequence. The selective attack at a single phosphanyl-alkyne moiety is observed. First a phosphirenium-borate zwitterion 15 is formed at r. t. Thermolysis (80 • C) results in the E-selective formation of the 1,1-carboboration product, the frustrated Lewis pair (FLP) E-16, which upon heating to 160 • C eventually undergoes isomerization followed by an internal nucleophilic aromatic substitution reaction to give the product 17 featuring a -B(F)(C 6 F 5 ) 2 substituent at the five-membered P-heterocycle. Finally, the FLP E-16 was reacted with n-butylisocyanide to yield the five-membered heterocyclic product 18, formed by P,B addition to the isonitrile carbon atom. Compounds 14, 15, 17, and 18 were characterized by X-ray crystal structure analyses.

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“…Phosphine-substituted boranes and boronate esters are particularly noteworthy for their application as organocatalysts or ligands in metal-catalyzed transformations. [12] In spite of the promising reactivity of these compounds, a limited variety of scaffolds have been explored due to the inability to readily access such molecular structures under the current methods.…”

Section: Tertiaryphosphineshaveplayedaprominentroleinthefieldmentioning

confidence: 99%

“…[11,12] To this end, deprotection of the phosphine in the presence of the boronate ester was investigated [Eq. (4)].…”

Section: Tertiaryphosphineshaveplayedaprominentroleinthefieldmentioning

confidence: 99%

Phosphine‐Directed CH Borylation Reactions: Facile and Selective Access to Ambiphilic Phosphine Boronate Esters

et al. 2014

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Ambiphilic ligands have received considerable attention over the last two decades due to their unique reactivity as organocatalysts and ligands. The iridium-catalyzed CÀH borylation of phosphines is described in which the phosphine is used as a directing group to provide selective formation of arylboronate esters with unique scaffolds of ambiphilic compounds. A variety of aryl and benzylic phosphines were subjected to the reaction conditions, selectively providing stable, isolable boronate esters upon protection of the phosphine as the borane complex. After purification, the phosphine-substituted boronate esters could be deprotected and isolated in pure form.

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On the Versatile and Unusual Coordination Behavior of Ambiphilic Ligands o-R₂P(Ph)BR‘₂

Abstract: Monophosphine-boranes were shown to behave as bidentate ambiphilic ligands, whose structural versatility has been illustrated by the preparation of PdII and AuI complexes featuring unusual P --> M-Cl --> B and P --> M --> B interactions, respectively.

Cited by 244 publications

References 16 publications

Frustrierte Lewis‐Paare: metallfreie Wasserstoffaktivierung und mehr

Frustrierte Lewis‐Paare: metallfreie Wasserstoffaktivierung und mehr

Facile 1,1-Carboboration Reaction of a Diarylphosphino-substituted Conjugated Diyne with Tris(pentafluorophenyl)borane

Phosphine‐Directed CH Borylation Reactions: Facile and Selective Access to Ambiphilic Phosphine Boronate Esters

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