Monomeric (dialkylamino)boranes: a new and efficient boron source in palladium catalyzed C–B bond formation with aryl halides

Euzenat, Lisenn; Horhant, David; Ribourdouille, Yann; Duriez, Christophe; Alcaraz, Gilles; Vaultier, Michel

doi:10.1039/b306874a

Cited by 83 publications

(64 citation statements)

References 25 publications

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“…20,23,24 Interestingly, during the same period, G. Alcaraz et al had demonstrated interest in dialkylaminoboranes R 2 NBH 2 in pallado-catalyzed reactions. 33 By comparison, it is worth noting that in silane chemistry, the use of dihydrogenosilanes R 2 SiH 2 in place of tertiary hydrogenosilanes HSiR 3 led us to the discovery of Ru 2 H 4 (µ-η 2 :η 2 :η 2 :η 2 -SiH 4 )(PCy 3 ) 4 , the first complex incorporating the simplest silane trapped between two metals. 34 The stabilization occurred through multiple σ-Si-H bond interactions.…”

Section: Synthesis Of New Bis(dihydrogen) Complexes the Firstmentioning

confidence: 99%

Bis σ-Bond Dihydrogen and Borane Ruthenium Complexes: Bonding Nature, Catalytic Applications, and Reversible Hydrogen Release

2009

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Hydrogen, the simplest element in the periodic table, plays a tremendous role in organic and inorganic chemistry. For years, it was inconceivable that dihydrogen could be bound to a metal center without breaking the H-H bond. Thus, oxidative addition of H(2) was universally recognized as a key elementary step in hydrogenation processes. In 1984, Kubas and co-workers reported the first example of a complex in which dihydrogen was coordinated to a metal center without breaking of the H-H bond. This opened a new area in coordination chemistry: sigma-complexes were born, complementing the well-known Werner-type family of complexes. Since then, hundreds of stable dihydrogen complexes have been isolated, and their properties have been investigated in detail. By comparison, very little information is available for the analogous class of sigma-borane complexes, in which sigma-H-B bonds are complexed to a metal (in the manner of H-H bonds in sigma-dihydrogen complexes). Since the first example published in 1996 by Hartwig and co-workers, very few sigma-borane complexes have been isolated. Scientists have maintained a continuous interest in catalytic hydrogenation reactions. Almost a century ago, in 1912, Paul Sabatier, the father of the hydrogenation process, received the Nobel prize, and the selection of Noyori and Knowles in 2001 for their studies on enantioselective catalyzed hydrogenations amply demonstrates the ongoing importance of the field. Moreover, during the past decade, dihydrogen has attracted considerable attention as a possible "fuel of the future". This endeavor has furthered interest in sigma-borane complexes, as more and more evidence links their chemistry to that of amine-borane derivatives. Indeed, ammonia-borane (NH(3)BH(3)) is attracting significant interest for hydrogen storage applications. One of the main limitations is the lack of reversibility associated with the production of dehydrogenated (BNH)(x) materials. Of major importance will be a better understanding of the coordination of H(2) to a metal center, and more generally of the coordination of H-E bonds (E = B, C), which are likely to play a critical role in the reversible dehydrogenation process. In this Account, we review our recent results in the field of dihydrogen and borane activation, with a specific focus on the problem of reversible dehydrogenation pathways. We concentrate on the chemistry of ruthenium complexes incorporating two sigma-ligands: either two dihydrogen or two sigma-B-H bonds. We describe our synthetic strategies to prepare such unusual structures. Their characterization is discussed in detail, highlighting the importance of an experimental and theoretical approach (NMR, structural, and theoretical studies). Some catalytic applications are discussed and put into context, and their reactivity toward reversible hydrogen release is detailed.

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Section: Synthesis Of New Bis(dihydrogen) Complexes the Firstmentioning

confidence: 99%

Bis σ-Bond Dihydrogen and Borane Ruthenium Complexes: Bonding Nature, Catalytic Applications, and Reversible Hydrogen Release

2009

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“…[44] Also, amine-boranes are attracting considerable attention as potential hydrogen-storage materials. [45] Primary and secondary amine-borane adducts have previously been thermally dehydrocoupled at elevated temperatures (> 100 8C) to give cyclic aminoboranes [(R 2 BÀNR' 2 ) x ] (x = 2 or 3) and borazine [(RBÀNR') 3 ] derivatives.…”

Section: Catalytic Dehydrocoupling Of Group 13/group 15 Lewis Acid-bamentioning

confidence: 99%

Transition‐Metal‐Catalyzed Dehydrocoupling: A Convenient Route to Bonds between Main‐Group Elements

Clark

Lee

Manners

2006

Chemistry A European J

271

194

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Lebende Zellen können vollständig mit Oxidhüllen bedeckt werden, die aus modifizierten Titanalkoxiden hergestellt werden (siehe Bild). Die Hüllen isolieren das eingeschlossene Biomaterial effizient gegen die Umgebung. Die so gebildeten kolloidalen Systeme sind höchst biokompatibel; die anschließende Freisetzung der eingeschlossenen Zellen oder Wirkstoffe in Organismen ist durch Auflösen der Titanoxidnanopartikel möglich.

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“…Recently, we demonstrated the excellent ability of monomeric aminoboranes to react as BH sources for C sp 2 -B sp 2 bond formation in a metal-catalyzed process [12]. For our purpose, we naturally envisaged applying our palladium-catalyzed borylation reaction to 1-alkenyl halides.…”

Section: Resultsmentioning

confidence: 97%

Stereospecific palladium-catalyzed borylation reaction of 1-alkenyl halides with diispropylaminoborane

Euzenat

Horhant

Brielles

et al. 2005

Journal of Organometallic Chemistry

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Monomeric (dialkylamino)boranes: a new and efficient boron source in palladium catalyzed C–B bond formation with aryl halides

Cited by 83 publications

References 25 publications

Bis σ-Bond Dihydrogen and Borane Ruthenium Complexes: Bonding Nature, Catalytic Applications, and Reversible Hydrogen Release

Bis σ-Bond Dihydrogen and Borane Ruthenium Complexes: Bonding Nature, Catalytic Applications, and Reversible Hydrogen Release

Transition‐Metal‐Catalyzed Dehydrocoupling: A Convenient Route to Bonds between Main‐Group Elements

Stereospecific palladium-catalyzed borylation reaction of 1-alkenyl halides with diispropylaminoborane

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