Photochemische Erzeugung von Triphenylsilylborandiyl (C6H5)3SiB: aus Organosilylboranen

Pachaly, Bernd; West, Robert

doi:10.1002/ange.19840960624

Cited by 49 publications

(22 citation statements)

References 7 publications

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“…[3] Further experiments on borylenes involve the photogeneration of triphenylsilylborylene Ph 3 SiB from (Ph 3 Si) 3 B in a glass matrix and its addition to bis(trimethylsilyl)ethyne and insertion into a CÀO bond of THF. [4] Arylborylene was invoked as an intermediate in the reduction of arylboron dihalides that yield borafluorenyls by intramolecular insertion into a CÀC s bond. [5] Another arylborylene, TbtB (Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl), was concluded to be an intermediate in the photolysis of TbtB-(SeMe) 2 based on trapping with phenanthrenequinone to give dioxaborolene.…”

Section: Introductionmentioning

confidence: 99%

Computational Study of van der Waals Complexes between Borylenes and Hydrocarbons

Krasowska

Bettinger

2014

Chemistry A European J

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The addition of borylenes (RB) to prototypical carbon-carbon multiple bonds (ethyne, ethene) and the insertion into a C-H bond of methane involves weakly bound van der Waals complexes of the reaction partners according to computational chemistry methods. Geometries of all complexes were optimized using spin-component scaled second-order Møller-Plesset perturbation theory (SCS-MP2) in combination with a quadruple-ζ (def2-QZVP) basis set. Energies were further refined using the coupled-cluster (CCSD(T)) method in combination with basis sets up to quadruple-ζ quality (def2-QZVP and aug-cc-pVTZ). All of the complexes of borylenes studied correspond to shallow minima on their potential-energy surfaces. Borylene complexes with ethyne are the most stable and those with methane are the least stable ones. Aminoborylene complexes BNHR with ethyne and ethene are stabilized mainly by NH⋅⋅⋅π interactions. Symmetry-adapted perturbation theory (SAPT) was performed to analyze the nature of the interaction between borylene molecules and hydrocarbons. Most of the ethyne complexes are dominated by electrostatic interactions, whereas for most of the ethene and all of the methane complexes the interaction is mainly dispersive.

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Section: Introductionmentioning

confidence: 99%

Computational Study of van der Waals Complexes between Borylenes and Hydrocarbons

Krasowska

Bettinger

2014

Chemistry A European J

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“…Various more-or-less successful trapping approaches have been developed to substantiate their existence, some of which subsequently having been disputed. [2] These approaches include high-temperature reactions, [3] the photolytic cleavage of BÀE bonds, [4] and inter- [5] and intramolecular [6] reductive dehalogenation reactions, which all suffered either from 1) poor analytical data for the resulting species, 2) harsh reaction conditions, and/or 3) low selectivity and yields of isolated products. They all failed to provide the ultimate evidence for the existence of free borylenes.…”

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confidence: 99%

Trapping the Elusive Parent Borylene

et al. 2011

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The taming of borylene: Dehalogenation of BHCl2⋅IMe (IMe=1,3‐dimethylimidazol‐2‐ylidene) leads to a carbene‐stabilized elusive BH borylene. A syn‐selective [2+1] cycloaddition with naphthalene enabled the isolation and full characterization of the resulting diastereomeric products. These findings along with calculations provide clear evidence for the existence of borylenes (crystal structures: B violet, C black, H gray, N blue).

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“…Diverse mehr oder minder erfolgreiche Abfangreaktionen, welche die Existenz freier Borylene belegen sollten, wurden seither entwickelt, von denen jedoch einige im Nachhinein widerrufen wurden. [2] Hierzu zählen unter anderem Hochtemperaturverfahren, [3] die photolytisch induzierte Spaltung von B-E-Bindungen [4] sowie inter- [5] und intramolekulare [6] reduktive Enthalogenierungen. Alle diese Strategien zeigen jedoch deutliche Schwächen im Hinblick auf einen oder mehrere der folgenden Aspekte: 1) Analytik der erhaltenen Produkte, 2) extreme Reaktionsbedingungen, 3) geringe Selektivitäten und Ausbeuten.…”

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