Borane
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Protodeboronation of Heteroaromatic, Vinyl, and Cyclopropyl Boronic Acids: pH–Rate Profiles, Autocatalysis, and Disproportionation Open
pH-rate profiles for aqueous-organic protodeboronation of 18 boronic acids, many widely viewed as unstable, have been studied by NMR and DFT. Rates were pH-dependent, and varied substantially between the boronic acids, with rate maxima tha…
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Activatable Photoacoustic Nanoprobes for In Vivo Ratiometric Imaging of Peroxynitrite Open
Organic semiconducting nanoprobes doped with bulky borane can undergo specific activation by ONOO- even at tumor-relevant acidic pH (6.8), permitting in vivo ratiometric photoacoustic imaging of ONOO- in the tumor environment of living mic…
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Covalent triazine framework supported non-noble metal nanoparticles with superior activity for catalytic hydrolysis of ammonia borane: from mechanistic study to catalyst design Open
Development of non-noble metal catalysts with similar activity and stability to noble metals is of significant importance in the conversion and utilization of clean energies.
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Tris(pentafluorophenyl)borane and Beyond: Modern Advances in Borylation Chemistry Open
As main-group chemistry, in particular boron chemistry, has expanded and developed over the past 20 years, one reagent has risen to prominence as well. Tris(pentafluorophenyl)borane, B(C6F5)3 (commonly known as BCF), has demonstrated exten…
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Bi(I)-Catalyzed Transfer-Hydrogenation with Ammonia-Borane Open
A catalytic transfer-hydrogenation utilizing a well-defined Bi(I) complex as catalyst and ammonia-borane as transfer agent has been developed. This transformation represents a unique example of low-valent pnictogen catalysis cycling betwee…
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Moisture-Tolerant Frustrated Lewis Pair Catalyst for Hydrogenation of Aldehydes and Ketones Open
In this paper, we report on the development of a bench-stable borane for frustrated Lewis pair catalyzed reduction of aldehydes, ketones, and enones. The deliberate fine-tuning of structural and electronic parameters of Lewis acid componen…
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Facile Synthesis of Three‐Dimensional Pt‐TiO<sub>2</sub> Nano‐networks: A Highly Active Catalyst for the Hydrolytic Dehydrogenation of Ammonia–Borane Open
Three‐dimensional (3D) porous metal and metal oxide nanostructures have received considerable interest because organization of inorganic materials into 3D nanomaterials holds extraordinary properties such as low density, high porosity, and…
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CuNi Nanoparticles Assembled on Graphene for Catalytic Methanolysis of Ammonia Borane and Hydrogenation of Nitro/Nitrile Compounds Open
Here we report a solution phase synthesis of 16 nm CuNi nanoparticles (NPs) with the Cu/Ni composition control. These NPs are assembled on graphene (G) and show Cu/Ni composition-dependent catalysis for methanolysis of ammonia borane (AB) …
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Palladium/Graphitic Carbon Nitride (g‐C<sub>3</sub>N<sub>4</sub>) Stabilized Emulsion Microreactor as a Store for Hydrogen from Ammonia Borane for Use in Alkene Hydrogenation Open
Direct hydrogenation of C=C double bonds is a basic transformation in organic chemistry which is vanishing from simple practice because of the need for pressurized hydrogen. Ammonia borane (AB) has emerged as a hydrogen source through its …
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Construction of σ-Aromatic AlB<sub>2</sub>Ring via Borane Coupling with a Dicoordinate Cyclic (Alkyl)(Amino)Aluminyl Anion Open
Since the groundbreaking discovery in 2018 that the synthesis of a bottleable nucleophilic aluminyl anion is feasible, a handful of derivatives have been developed to date, which are, however, limited to diamino- and dialkyl-substituted sp…
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Modulating Electronic Metal‐Support Interactions to Boost Visible‐Light‐Driven Hydrolysis of Ammonia Borane: Nickel‐Platinum Nanoparticles Supported on Phosphorus‐Doped Titania Open
Ammonia borane (AB) is a promising material for chemical H 2 storage owing to its high H 2 density (up to 19.6 wt %). However, the development of an efficient catalyst for driving H 2 evolution through AB hydrolysis remains challenging. Th…
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Highly Active Iron Catalyst for Ammonia Borane Dehydrocoupling at Room Temperature Open
The iron complex [FeH(CO) (PNP)] (PNP = N-(CH(2)CH(2)PiPr(2))(2)) is a highly active catalyst for ammonia borane dehydrocoupling at room temperature. Mainly linear polyaminoborane is obtained upon release of 1 equiv of H-2. Mechanistic stu…
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Group 6 Transition‐Metal/Boron Frustrated Lewis Pair Templates Activate N<sub>2</sub>and Allow its Facile Borylation and Silylation Open
The reaction of trans ‐[M(N 2 ) 2 (dppe) 2 ] (M=Mo, 1 Mo , M=W, 1 W ) with B(C 6 F 5 ) 3 ( 2 ) provides the adducts [(dppe) 2 M=N=N‐B(C 6 F 5 ) 3 ] ( 3 ) which can be regarded as M/B transition‐metal frustrated Lewis pair (TMFLP) templates…
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Amine–Boranes as Transfer Hydrogenation and Hydrogenation Reagents: A Mechanistic Perspective Open
Transfer hydrogenation (TH) has historically been dominated by Meerwein–Ponndorf–Verley (MPV) reactions. However, with growing interest in amine–boranes, not least ammonia–borane (H 3 N⋅BH 3 ), as potential hydrogen storage materials, thes…
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Recent Advances and Perspectives on Supported Catalysts for Heterogeneous Hydrogen Production from Ammonia Borane Open
Ammonia borane (AB), a liquid hydrogen storage material, has attracted increasing attention for hydrogen utilization because of its high hydrogen content. However, the slow kinetics of AB hydrolysis and the indefinite catalytic mechanism r…
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Hydroboration of Carbon Dioxide Using Ambiphilic Phosphine–Borane Catalysts: On the Role of the Formaldehyde Adduct Open
Ambiphilic phosphine–borane derivatives 1-B(OR)2-2-PR′2–C6H4 (R′ = Ph (1), iPr (2); (OR)2 = (OMe)2 (1a, 2a); catechol (1b, 2b) pinacol (1c, 2c), −OCH2C(CH3)2CH2O– (1d)) were tested as catalysts for the hydroboration of CO2 using HBcat or B…
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Tailoring Surface Frustrated Lewis Pairs of In<sub>2</sub>O<sub>3−</sub><i><sub>x</sub></i>(OH)<sub>y</sub> for Gas‐Phase Heterogeneous Photocatalytic Reduction of CO<sub>2</sub> by Isomorphous Substitution of In<sup>3+</sup> with Bi<sup>3+</sup> Open
Frustrated Lewis pairs (FLPs) created by sterically hindered Lewis acids and Lewis bases have shown their capacity for capturing and reacting with a variety of small molecules, including H 2 and CO 2 , and thereby creating a new strategy f…
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Tris(2,4,6‐trifluorophenyl)borane: An Efficient Hydroboration Catalyst Open
The metal‐free catalyst tris (2,4,6‐trifluorophenyl)borane has demonstrated its extensive applications in the 1,2‐hydroboration of numerous unsaturated reagents, namely alkynes, aldehydes and imines, consisting of a wide array of electron‐…
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A catalytic fluoride-rebound mechanism for C(sp <sup>3</sup> )-CF <sub>3</sub> bond formation Open
Trifluoromethylation via broken C-F bonds Trifluoromethyl substituents are widely used in pharmaceutical research to tune the properties of drug candidates. Generally, they are introduced intact through the formation of carbon-carbon bonds…
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P–N Cooperative Borane Activation and Catalytic Hydroboration by a Distorted Phosphorous Triamide Platform Open
Studies of the stoichiometric and catalytic reactivity of a geometrically constrained phosphorous triamide 1 with pinacolborane (HBpin) are reported. The addition of HBpin to phosphorous triamide 1 results in cleavage of the B-H bond of pi…
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Copper‐Catalyzed Borylative Cross‐Coupling of Allenes and Imines: Selective Three‐Component Assembly of Branched Homoallyl Amines Open
A copper‐catalyzed three‐component coupling of allenes, bis(pinacolato)diboron, and imines allows regio‐, chemo‐, and diastereoselective assembly of branched α,β‐substituted‐γ‐boryl homoallylic amines, that is, products bearing versatile a…
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Amine–Borane Dehydropolymerization: Challenges and Opportunities Open
The dehydropolymerization of amine–boranes, exemplified as H 2 RB⋅NR′H 2 , to produce polyaminoboranes (HRBNR′H) n that are inorganic analogues of polyolefins with alternating main‐chain B−N units, is an area with significant potential, st…
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Direct and Transfer Hydrosilylation Reactions Catalyzed by Fully or Partially Fluorinated Triarylboranes: A Systematic Study Open
The present survey serves several purposes. Selected electron-deficient boron Lewis acids catalyze the release of hydrosilanes from cyclohexa-2,5-dien-1-yl-substituted silanes. The two-step process consists of a hydride abstraction to gene…
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Role of Pressure in the Growth of Hexagonal Boron Nitride Thin Films from Ammonia-Borane Open
We analyze the optical, chemical, and electrical properties of chemical vapor\ndeposition (CVD) grown hexagonal boron nitride (h-BN) using the precursor\nammonia-borane ($H_3N-BH_3$) as a function of $Ar/H_2$ background pressure\n($P_{TOT}…
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Catalytic B–N Dehydrogenation Using Frustrated Lewis Pairs: Evidence for a Chain-Growth Coupling Mechanism Open
The catalytic dehydrogenation of ammonia- and amine-boranes by a dimethylxanthene-derived frustrated Lewis pair is described. Turnover is facilitated on a thermodynamic basis by the ready release of H2 from the weakly basic PPh2-containing…
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Mesoporous Silica-Supported Amidozirconium-Catalyzed Carbonyl Hydroboration Open
The hydroboration of aldehydes and ketones using a silica-supported zirconium catalyst is reported. Reaction of Zr(NMe2)4 and mesoporous silica nanoparticles (MSN) provides the catalytic material Zr(NMe2)n@MSN. Exhaustive characterization …
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Functional group migrations between boron and metal centres within transition metal–borane and –boryl complexes and cleavage of H–H, E–H and E–E′ bonds Open
This review looks at the migration of functional groups between metal and boron centres and the activation of element–element bonds in transition metal–borane and –boryl complexes.
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Ceria-supported ruthenium nanoparticles as highly active and long-lived catalysts in hydrogen generation from the hydrolysis of ammonia borane Open
Ruthenium(0) nanoparticles supported on ceria (Ru0/CeO2) were in situ generated from the reduction of ruthenium(iii) ions impregnated on ceria during the hydrolysis of ammonia borane.
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Alkene–Carbene Isomerization induced by Borane: Access to an Asymmetrical Diborene Open
A 2,3-dihydro-1H-1,2-azaborole derivative 2 was converted to a cyclic (alkyl) (amino)carbene (cAAC) via 1,2-hydrogen migration triggered by boranes to afford cAAC-borane adducts. This procedure allowed us to develop an asymmetrical diboren…
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Tris(perfluorotolyl)borane—A Boron Lewis Superacid Open
Tris[tetrafluoro‐4‐(trifluoromethyl)phenyl]borane (BTolF) was prepared by treating boron tribromide with tetrameric F 3 CC 6 F 4 ‐Cu I . The F 3 CC 6 F 4 ‐Cu I was generated from F 3 CC 6 F 4 MgBr and copper(I) bromide. Lewis acidities of …