915703-83-2

Upstream product

• 915703-81-0 N,N'-bis(2,6-diisopropylphenyl)-2-bromo-2,3-dihydro-1H-1,3,2-diazaborole 
• 100-52-7 benzaldehyde 
• 948054-44-2 lithium 1,3-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaborol-2-ide 
• 7732-18-5 water 
• 7439-93-2 lithium 
• 16853-85-3 lithium aluminium tetrahydride 
• 110-71-4 1,2-dimethoxyethane 
• 97510-97-9 (((6-iodohexyl)oxy)methyl)benzene 
• 71-43-2 benzene 
• 10025-78-2 trichlorosilane 
• 74-94-2 dimethylamine borane 
• 7699-45-8 zinc dibromide 
• 7646-85-7 zinc(II) chloride 
• 7664-41-7 ammonia 

Downstream Products

• 1082608-24-9 PhCH₂[B(NDipCH)₂] 

Relevant academic research and scientific papers

Synthesis, structure of borylmagnesium, and its reaction with benzaldehyde to form benzoylborane

The reaction of boryllithium 2 with 1.0 or 0.5 equiv of MgBr2·OEt2 provided boryl Grignard reagents, borylmagnesium bromides 3 and 4, or bis(boryl)magnesium 5. Structures of 3, 4, and 5 in the crystals and solutions indicated the ionic character of the B-

Group-4 transition-metal boryl complexes: Syntheses, structures, boron-metal bonding properties, and application as a polymerization catalyst

(Chemical Equation Presented) Two group-4 boryl complexes, boryltitanium 2 and borylhafnium 3, were synthesized via nucleophilic borylation using boryllithium 1. Complexes 2 and 3 are the first examples of group-4 borylmetals. Theoretical calculations on

Approaching a “Naked” Boryl Anion: Amide Metathesis as a Route to Calcium, Strontium, and Potassium Boryl Complexes

Amide metathesis has been used to generate the first structurally characterized boryl complexes of calcium and strontium, {(Me3Si)2N}M{B(NDippCH)2}(thf)n (M=Ca, n=2; M=Sr, n=3), through the reactions of the corresponding bis(amides), M{N(SiMe3)2}2(thf)2, with (thf)2Li- {B(NDippCH)2}. Most notably, this approach can also be applied to the analogous potassium amide K{N(SiMe3)2}, leading to the formation of the solvent-free borylpotassium dimer [K{B(NDippCH)2}]2, which is stable in the solid state at room temperature for extended periods (48 h). A dimeric structure has been determined crystallographically in which the K+ cations interact weakly with both the ipso-carbons of the flanking Dipp groups and the boron centres of the diazaborolyl heterocycles, with K???B distances of >3.1 ?. These structural features, together with atoms in molecules (QTAIM) calculations imply that the boron-containing fragment closely approaches a limiting description as a “free” boryl anion in the condensed phase.

Reaction of a boryl anion with silicon halides and alkoxysilanes: Synthesis of borylsilanes

The reactions of boryl anion [(CH)2(NDipp)2]BLi (Dipp = 2,6-iPr2C6H3) (1) with a series of silicon halides and alkoxysilanes were investigated. Treatment of 1 with SiCl4 and PhSiCl3 afforded corresponding borylsilanes [(CH)2(NDipp)2]BSiCl3 (2) and [(CH)2(NDipp)2]BSiPhCl2 (3), respectively, in good yields. Reaction of HSiCl3 with 1 yielded a mixture of [(CH)2(NDipp)2]BSiHCl2 (4) and [(CH)2(NDipp)2]BH whereas the similar reaction with PhSiHCl2 yielded the borylsilane [(CH)2(NDipp)2]BSiPhHCl (5) as a sole product. In contrast, reaction of 1 with SiBr4 led to the reduction of SiBr4 with the formation of [(CH)2(NDipp)2]BBr and the expected substituted product [(CH)2(NDipp)2]BSiBr3 (6) was not formed. Reaction of alkoxysilane RSi(OMe)3 (R = H, Ph, Np, OMe) with 1 exclusively yielded the substituted product [(CH)2(NDipp)2]BSiR(OMe)2 (7a-d), which reacted with BBr3 to give the bromides [(CH)2(NDipp)2]BSiRBr2 (8a-c, R = H, Ph, Np) and [(CH)2(NDipp)2]BSiBr3 (6, R = OMe). These products have been characterized spectroscopically as well as X-ray single-crystal analysis in some cases.

An Acid-Free Anionic Oxoborane Isoelectronic with Carbonyl: Facile Access and Transfer of a Terminal B=O Double Bond

We disclose the synthesis and structural characterization of the first acid-free anionic oxoborane, [K(2.2.2-crypt)][(HCDippN)2BO] (1) (Dipp = 2,6-iPr2C6H3), which is isoelectronic with classical carbonyl compounds. 1 can readily be accessed from its borinic acid by a simple deprotonation/sequestration sequence. Crystallographic and density functional theory (DFT) analyses support the presence of a polarized terminal B?O double bond. Subsequent π bond metathesis converts the B?O bond to a heavier B?S containing system, affording the first anionic thioxoborane [K(2.2.2-crypt)][(HCDippN)2BS] (2), isoelectronic with thiocarbonyls. Facile B=O bond cleavage can also be achieved to access B-H and B-Cl bonds and, via a remarkable oxide (O2-) ion abstraction, to generate a borenium cation [(HCDippN)2B(NC5H5)][OTf] (4). By extension, 1 can act as an oxide transfer agent to organic substrates, a synthetic role traditionally associated with transition-metal compounds. Hence we show that B-O linkages, which are often considered to be thermodynamic sinks, can be activated under mild conditions toward bond cleavage and transfer, by exploiting the higher reactivity inherent in the B=O double bond.

Electronic Delocalization in Two and Three Dimensions: Differential Aggregation in Indium “Metalloid” Clusters

Reduction of indium boryl precursors to give two- and three-dimensional M?M bonded networks is influenced by the choice of supporting ligand. While the unprecedented nanoscale cluster [In68(boryl)12]? (with an In12@In44@In12(boryl)12 concentric structure), can be isolated from the potassium reduction of a bis(boryl)indium(III) chloride precursor, analogous reduction of the corresponding (benzamidinate)InIIIBr(boryl) system gives a near-planar (and weakly aromatic) tetranuclear [In4(boryl)4]2? system.

A Combined Experimental/Computational Study of the Mechanism of a Palladium-Catalyzed Bora-Negishi Reaction

Experimental and computational efforts are reported which illuminate the mechanism of a novel boron version of the widespread Negishi coupling reaction that offers a new protocol for the formation of aryl/acyl C?B bonds using a bulky boryl fragment. The role of nucleophilic borylzinc reagents in the reduction of the PdII pre-catalysts to Pd0 active species has been demonstrated. The non-innocent behavior of the PPh3 ligands of the [Pd(PPh3)2Cl2] pre-catalyst under activation conditions has been probed both experimentally and computationally, revealing the formation of a trimetallic Pd species bearing bridging phosphide (PPh2?) ligands. Our studies also reveal the monoligated formulation of the Pd0 active species, which led us to synthesize related (η3-indenyl)Pd-monophosphine catalysts which show improved catalytic performances under mild conditions. A complete mechanistic proposal to aid future catalyst developments is provided.

Enabling and Probing Oxidative Addition and Reductive Elimination at a Group 14 Metal Center: Cleavage and Functionalization of E-H Bonds by a Bis(boryl)stannylene

By employing strongly σ-donating boryl ancillary ligands, the oxidative addition of H2 to a single site SnII system has been achieved for the first time, generating (boryl)2SnH2. Similar chemistry can also be achieved for protic and hydridic E-H bonds (N-H/O-H, Si-H/B-H, respectively). In the case of ammonia (and water, albeit more slowly), E-H oxidative addition can be shown to be followed by reductive elimination to give an N- (or O-)borylated product. Thus, in stoichiometric fashion, redox-based bond cleavage/formation is demonstrated for a single main group metal center at room temperature. From a mechanistic viewpoint, a two-step coordination/proton transfer process for N-H activation is shown to be viable through the isolation of species of the types Sn(boryl)2·NH3 and [Sn(boryl)2(NH2)]- and their onward conversion to the formal oxidative addition product Sn(boryl)2(H)(NH2).

Catalytic Borylation using an Air-Stable Zinc Boryl Reagent: Systematic Access to Elusive Acylboranes

The use of borylzinc reagents in palladium-catalyzed borylation chemistry is described (i.e. a boron analogue of the Negishi coupling), including a one-pot bench-top protocol using an air- and moisture-stable bis(boryl)zinc reagent. The steric/electronic properties of the boryl fragment employed enable a systematic method for accessing acylboranes, a rare class of organoboron species with great potential in chemical synthesis. The reactions proceed under mild conditions, use inexpensive commercial sources of palladium, and demonstrate a remarkable functional-group tolerance.

Beryllium bis(diazaborolyl): Old neighbors finally shake hands

The synthesis of a linear beryllium bis(diazaborolyl) compound featuring the first non-cluster bond between boron and beryllium has been achieved through the reaction of Yamashita's lithium diazaborolide and BeCl2. In accord with the established chemistry of beryllium, the bonding is polar covalent in character, as determined by structural and spectroscopic analysis, as well as reactivity studies.