A computational study on the capability of borane‐cyclic boryl anion adducts to act as hydrogen atom donors

Lai, Chin‐Hung; Chou, Pi‐Tai

doi:10.1002/jcc.21515

Cited by 11 publications

(8 citation statements)

References 22 publications

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“…NHC-boranes 2 are an emerging class of reagents with applications in ionic, organometallic, and radical reactions . Thus, we felt that compounds like 4 were doubly interesting as boryl-substituted borohydrides and as anionic analogs of neutral NHC-boranes . According to the latter analogy, anions like 4 can also be viewed as unusual examples of complexes between a boron-derived Lewis acid (BH 3 ) and a boron-derived Lewis base ( 3 ).…”

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confidence: 99%

Boryltrihydroborate: Synthesis, Structure, and Reactivity as a Reductant in Ionic, Organometallic, and Radical Reactions

et al. 2010

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Reaction of lithium 1,3-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaborol-2-ide with borane.THF provides the first boryl-substituted borohydride: lithium [1,3-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaborol-2-yl]trihydroborate. The compound is fully characterized by (11)B, (1)H, and (7)Li NMR spectra and other means, and these data are compared to neutral and anionic benchmark compounds. The compound crystallizes as a dimer complexed to four THF molecules. The dimer lacks the bridging B-H bonds seen in neutral boranes and is instead held together by ionic Li---HB interactions. A preliminary scan of reactions with several iodides shows that the compound participates in an ionic reduction (with a primary-alkyl iodide), an organometallic reduction (Pd-catalyzed with an aryl iodide), and a radical reduction (AIBN-initiated with a sugar-derived iodide). Accordingly the new borylborohydride class may share properties of both traditional borohydrides and isoelectronic N-heterocyclic carbene boranes.

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confidence: 99%

Boryltrihydroborate: Synthesis, Structure, and Reactivity as a Reductant in Ionic, Organometallic, and Radical Reactions

et al. 2010

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“…43 and 44 do not have conjugation at the boron part at all, thus their electrophilicity indices (5.44 and 5.41 eV) are both smaller than that of no. 35. In comparison, 5a), a result of their definition.…”

Section: The Journal Of Organic Chemistrymentioning

confidence: 99%

“…Density functional theory (DFT) based calculations were carried out by using the Gaussian 09 package at the (U)MPW1K/6-31+G(d) level for all molecular species under the ideal gas assumption. This model chemistry has been proven to be able to accurately describe the geometries of zwitterions (i.e., LB stabilized boryl radicals). − ,− For each species, a geometry optimization followed by a frequency calculation using the harmonic oscillator model was employed to identify stable minimum energy structure.…”

Section: Theoretical Calculationsmentioning

confidence: 99%

Electrophilicity and Nucleophilicity of Boryl Radicals

Hou

Zheng

et al. 2017

J. Org. Chem.

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We carried out a survey of the relative reactivity of a collection of 91 neutral boryl radicals using density functional calculations. Their reactivities were characterized by four indices, i.e., the global electrophilicity, global nucleophilicity, local electrophilicity, and local nucleophilicity. Particularly, the global electrophilicity and nucleophilicity indices span over a moderately wider range than those of carbon radicals, indicating their potentially broader reactivity. Thus, boryl radicals may be utilized in electrophilic radical reactions, while traditionally they are only considered for nucleophilic radical reactions. In contrast, the local electrophilicity and nucleophilicity indices at the boron center show a different reactivity picture than their global counterparts. The inconsistency is rooted in the low and varying spin density on boron (for most radicals, less than 50%) in different boryl radicals, which is a combinative result of radical stabilization via electron delocalization and the low electronegativity of boron (compared to carbon). In short, the boron character in boryl radicals may be weak and their reactivity is not reflected by the local indices based on boron but by the global ones.

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“…Überraschend ist das nicht, denn 68 ist letztlich immer noch ein Borhydrid. Rechnungen zufolge hat 68 eine schwache B-H-Bindung, [63] und nach ersten Untersuchungen kann es sowohl an radikalischen als auch ionischen und metallorganischen Reaktionen teilnehmen. [62] …”

Section: P Curran Et Alunclassified

Komplexe von N‐heterocyclischen Carbenen mit Boranen: Synthese und Reaktionen

et al. 2011

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Borane sind weit verbreitete Lewis‐Säuren, und N‐heterocyclische Carbene (NHCs) sind beliebte Lewis‐Basen. Dennoch war bis in die jüngste Zeit erstaunlich wenig über Komplexe dieser beiden Verbindungsklassen miteinander bekannt. NHC‐Borane sind leicht herzustellen, und teilweise sind sie so stabil, dass sie weniger als Komplex, sondern vielmehr als eigenständige organische Verbindung betrachtet werden können. Sie verhalten sich nicht wie klassische Borane, und sie können ein breites Spektrum an funktionellen Gruppen enthalten. Als vielseitige Reaktionspartner, Reagentien und Katalysatoren verfügen NHC‐Borane über ein immenses Potenzial für die organische Synthese und die Polymerchemie. Viele Reaktionen von NHC‐Boranen laufen über neue reaktive Intermediate wie Boreniumkationen, Borylradikale und sogar Borylanionen ab. Hier geben wir eine umfassende Übersicht über die Synthese, Charakterisierung und Reaktionen von NHC‐Boranen.

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A computational study on the capability of borane‐cyclic boryl anion adducts to act as hydrogen atom donors

Cited by 11 publications

References 22 publications

Boryltrihydroborate: Synthesis, Structure, and Reactivity as a Reductant in Ionic, Organometallic, and Radical Reactions

Boryltrihydroborate: Synthesis, Structure, and Reactivity as a Reductant in Ionic, Organometallic, and Radical Reactions

Electrophilicity and Nucleophilicity of Boryl Radicals

Komplexe von N‐heterocyclischen Carbenen mit Boranen: Synthese und Reaktionen

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