[Ir(PCy3)2(H)2(H2BNMe2)]+ as a Latent Source of Aminoborane: Probing the Role of Metal in the Dehydrocoupling of H3B⋅NMe2H and Retrodimerisation of [H2BNMe2]2

Stevens, Charlotte J.; Dallanegra, Romaeo; Chaplin, Adrian B.; Weller, Andrew S.; Macgregor, Stuart A.; Ward, Bryan J.; McKay, David; Alcaraz, Gilles; Sabo-Étienne, Sylviane

doi:10.1002/chem.201002517

Cited by 116 publications

(182 citation statements)

References 79 publications

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“…2.8.4) was developed (Scheme 3), suggesting that the formation of H 3 B · NMe 2 BH 2 · NMe 2 H is a metal-based process. The role of this diborazane in the dehydrocoupling of H 3 B · NMe 2 H has been further discussed by others [15,19,28,31,32].…”

Section: Aminoboranes: Observation and Trappingmentioning

confidence: 93%

“…The kinetics for the "off-metal" dimerisation of H 2 B¼NMe 2 to form [H 2 BNMe 2 ] 2 have been explored and found to be a second-order process with a large negative entropy of activation [19]. Interestingly, a significant solvent effect on the relative rate of dimerisation has also been noted, with acetonitrile accelerating the process [13,20].…”

Section: Aminoboranes: Observation and Trappingmentioning

confidence: 96%

“…These weak interactions arise primarily from donation from the σ B-H orbital to the metal; the B-H σ* orbital is high in energy, meaning that back-donation from the metal is negligible [11,61]. Often, sigma complexes are isolated using tertiary amine-boranes, Amine-boranes can also bind to the metal centre through two B-H sigma bonds, resulting in η 2 complexes [19,64,65]. Oligomeric species such as H 3 B · NMe 2 BH 2 · NMe 2 H have also been observed to bind in this manner (Fig.…”

Section: Sigma Complexes Of Amine-boranesmentioning

confidence: 99%

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The Catalytic Dehydrocoupling of Amine–Boranes and Phosphine–Boranes

Johnson

Hooper

Weller

2015

Topics in Organometallic Chemistry

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Section: Aminoboranes: Observation and Trappingmentioning

confidence: 93%

Section: Aminoboranes: Observation and Trappingmentioning

confidence: 96%

Section: Sigma Complexes Of Amine-boranesmentioning

confidence: 99%

See 1 more Smart Citation

The Catalytic Dehydrocoupling of Amine–Boranes and Phosphine–Boranes

Johnson

Hooper

Weller

2015

Topics in Organometallic Chemistry

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127

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“…[3] Moreover, as a consequence of the expanded interest in hydrogen release, the field of amineborane coordination chemistry is now under active development. [4] Discoveries in this new area promise improved fundamental understanding of the activation and transformation of these fascinating molecules at transition-metal centers, processes that appear central to both their dehydrogenation and polymerization chemistries.…”

mentioning

confidence: 99%

Advances with Ammonia‐Borane: Improved Recycling and Use as a Precursor to Atomically Thin BN Films

Whittell

Manners

2011

Angew Chem Int Ed

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ammonia-borane · boranes · boron nitride · hydrogen storage · hydrogenation Amine-boranes, exemplified by ammonia-borane (AB), H 3 N·BH 3 , represent some of the simplest and best-known inorganic molecules. Over the past decade these compounds have attracted considerable attention as portable hydrogen storage materials, due in the main part to their high gravimetric hydrogen contents (ca. 20 % by weight for AB).[1] This has motivated the development of new synthetic methods for convenient hydrogen release, and a variety of highly active catalysts that function under mild conditions are now known. These procedures have recently been adapted to allow the preparation of new polymeric materials. For example, polyaminoboranes, (RNH-BH 2 ) n , have been prepared by catalytic dehydrogenation of primary amine-boranes, such as MeNH 2 ·BH 3 .[2] Amine-boranes have also been widely used as reducing agents, including for the preparation of metal nanoparticles, and in hydrogen-transfer reactions involving organic substrates.[3] Moreover, as a consequence of the expanded interest in hydrogen release, the field of amineborane coordination chemistry is now under active development.[4] Discoveries in this new area promise improved fundamental understanding of the activation and transformation of these fascinating molecules at transition-metal centers, processes that appear central to both their dehydrogenation and polymerization chemistries.The dehydrogenation of AB [1] may be viewed in terms of three distinct exergonic steps, each associated with the loss of one equivalent of hydrogen. The challenge with developing AB as a practical hydrogen-storage material therefore lies not only in the liberation of hydrogen but also in the regeneration of the spent fuel. Furthermore, this problem becomes particularly acute if the reaction proceeds with complete dehydrogenation to form boron nitride, which is thermodynamically very stable.In practice, the near-ambient-temperature routes to dehydrogenate AB do not result in the formation of boron nitride but yield a spent fuel whose precise nature depends on the method of hydrogen release. Polyborazylene (BNH x (0 < x < 2), Scheme 1) functions as a model for such species, as it contains the fused borazine rings and BÀH and NÀH bonds that should be common to any dehydrogenated material. A viable synthetic route to convert polyborazylene back to AB would therefore have important implications for the feasibility of using the latter for hydrogen storage.An impressive recent advance by Gordon and co-workers describes the successful conversion of polyborazylene to AB upon treatment with hydrazine in liquid ammonia.[5] Polyborazylene was found to react with hydrazine at room temperature to afford predominantly hydrazine-borane. Exchange of the hydrazine in this compound for ammonia, however, could not be achieved at this temperature owing to the greater thermodynamic stability of the hydrazine adduct. Heating to 60 8C was therefore employed to cleave the BÀN bond and afford AB by combination of the l...

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“…[3] Außerdem erfährt die Aminboran-Koordinationschemie infolge des steigenden Interesses an der Wasserstoff-Freisetzung derzeit einen regen Aufschwung. [4] Die Entdeckungen auf diesem neuen Gebiet versprechen ein verbessertes Verständnis der Aktivierung und Transformation dieser faszinierenden Moleküle an Übergangsmetallzentren, die zentrale Vorgänge sowohl bei ihrer Dehydrierung als auch bei ihrer Polymerisation sind.…”

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Fortschritte bei Ammoniak‐Boran: verbessertes Recycling und Einsatz als Vorstufe für BN‐Einzelschichten

Whittell

Manners

2011

Angewandte Chemie

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[Ir(PCy₃)₂(H)₂(H₂BNMe₂)]⁺ as a Latent Source of Aminoborane: Probing the Role of Metal in the Dehydrocoupling of H₃B⋅NMe₂H and Retrodimerisation of [H₂BNMe₂]₂

Cited by 116 publications

References 79 publications

The Catalytic Dehydrocoupling of Amine–Boranes and Phosphine–Boranes

The Catalytic Dehydrocoupling of Amine–Boranes and Phosphine–Boranes

Advances with Ammonia‐Borane: Improved Recycling and Use as a Precursor to Atomically Thin BN Films

Fortschritte bei Ammoniak‐Boran: verbessertes Recycling und Einsatz als Vorstufe für BN‐Einzelschichten

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