Synthesis and structure of novel polycyclic species from toluene and m-xylene and the dehalogenation product of difluoro(diisopropylamino)borane

Meller, A.; Seebold, U.; Maringgele, W.; Noltemeyer, Mathias; Sheldrick, George M.

doi:10.1021/ja00203a052

Cited by 42 publications

(12 citation statements)

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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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confidence: 99%

Trapping the Elusive Parent Borylene

et al. 2011

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“…In such reduction reactions the initial formation of a free arylborylene was postulated, followed by its intramolecular insertion into C-C bonds of the aryl substituent (Figure 24, A). The extreme reactivity of free borylenes was even more strikingly demonstrated by Meller and coworkers 254,255 when they demonstrate that the borylenes generated from the reduction of X2BNiPr2 (X = F, Cl) react even with toluene and other arenes to give various ring-expansion products (Figure 24, B). (Figure 25), via the photolysis of PhB(N3)2.…”

Section: Monocoordinate Borylenesmentioning

confidence: 93%

Metallomimetic Chemistry of Boron

2019

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The study of main-group molecules that behave and react similarly to transition metal (TM) complexes has attracted significant interest in the recent decades. Most notably, the attractive idea of eliminating the all-too-often rare and costly metals from catalysis has motivated efforts to develop main-group-element-mediated reactions. Main-group elements, however, lack the electronic flexibility of many TM complexes that arise from combinations of empty and filled d-orbitals and that seem ideally suited to bind and activate many substrates. In this Review, we look at boron, an element which, despite its non-metal nature, low atomic weight, and relative redox staticity has achieved great milestones in terms of TM-like reactivity. We show how in inter-element cooperative systems, diboron molecules and hypovalent complexes, the fifth element can acquire a truly metallomimetic character. As we discuss, this character is particularly strikingly demonstrated by the reactivity of boron-based molecules with H2, CO, alkynes, alkenes and even with N2.

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“…Strikingly, different results are obtained [18] from reactions of the diisopropylaminoboron difluoride, (Me 2 CH) 2 NBF 2 , Na/K system in 1,2-dimethoxyethane (DME) with toluene, m-xylene, benzene, and naphthalene. The products, whose structures in the case of toluene and xylene were determined by X-ray crystallography, are the result of multiple insertions of the (Me 2 CH) 2 NB: fragment between the aromatic ring carbons, forming products in which the borons are tricoordinate.…”

Section: Introductionmentioning

confidence: 99%