915703-83-2Relevant articles and documents
Synthesis, structure of borylmagnesium, and its reaction with benzaldehyde to form benzoylborane
Yamashita, Makoto,Suzuki, Yuta,Segawa, Yasutomo,Nozaki, Kyoko
, p. 9570 - 9571 (2007)
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-
Approaching a “Naked” Boryl Anion: Amide Metathesis as a Route to Calcium, Strontium, and Potassium Boryl Complexes
Protchenko, Andrey V.,Vasko, Petra,Fuentes, M. ángeles,Hicks, Jamie,Vidovic, Dragoslav,Aldridge, Simon
supporting information, p. 2064 - 2068 (2020/11/30)
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.
An Acid-Free Anionic Oxoborane Isoelectronic with Carbonyl: Facile Access and Transfer of a Terminal B=O Double Bond
Loh, Ying Kai,Porteous, Kieran,Fuentes, M. Angeles,Do, Dinh Cao Huan,Hicks, Jamie,Aldridge, Simon
supporting information, p. 8073 - 8077 (2019/06/10)
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
Protchenko, Andrey V.,Urbano, Juan,Abdalla, Joseph A. B.,Campos, Jesús,Vidovic, Dragoslav,Schwarz, Andrew D.,Blake, Matthew P.,Mountford, Philip,Jones, Cameron,Aldridge, Simon
supporting information, p. 15098 - 15102 (2017/10/18)
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.
