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.
Reaction of a boryl anion with silicon halides and alkoxysilanes: Synthesis of borylsilanes
Liu, Zhaocai,Cui, Chunming
, (2019/12/09)
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.
A Combined Experimental/Computational Study of the Mechanism of a Palladium-Catalyzed Bora-Negishi Reaction
Campos, Jesús,Nova, Ainara,Kolychev, Eugene L.,Aldridge, Simon
supporting information, p. 12655 - 12667 (2017/09/18)
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.