Homolytic, Heterolytic, Mesolytic - As You Like It: Steering the Cleavage of a HC(sp(3))-C(sp(3))H Bond in Bis(1H-2,1-benzazaborole)Derivatives

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F16%3A39902111" target="_blank" >RIV/00216275:25310/16:39902111 - isvavai.cz</a>

Result on the web

<a href="http://dx.doi.org/10.1002/chem.201602698" target="_blank" >http://dx.doi.org/10.1002/chem.201602698</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/chem.201602698" target="_blank" >10.1002/chem.201602698</a>

Result language

angličtina

Original language name

Homolytic, Heterolytic, Mesolytic - As You Like It: Steering the Cleavage of a HC(sp(3))-C(sp(3))H Bond in Bis(1H-2,1-benzazaborole)Derivatives

Original language description

A set of (3,3')-bis(1-Ph-2-R-1H-2,1-benzazaborole) compounds, in which R= tBu (Bab-tBu)(2), R= Dipp (BabDipp)2 or R= tBu and Dipp (Bab-Dipp)(Bab-tBu), was synthesized and fully characterized using H-1, B-11, C-13, and N-15 NMR spectroscopy as well as single-crystal X-ray diffraction analysis. The central HC(sp(3))-C(sp(3)) H bond with restricted rotation at the junction of both 1H-2,1-benzazaborole rings displayed an intriguing reactivity. It was demonstrated that this bond is easily mesolytically cleaved using alkali metals to form the respective aromatic 1Ph-2R-1H-2,1-benzazaborolyl anions M+(THF)(n)(Bab-tBu)(-)(M= Li, Na, K) and K+ (THF)(n)(Bab-Dipp)(-). Furthermore, the central HC(sp(3))-C(sp(3)) H bond of bis(1H-2,1-benzazaborole)s is also homolytically cleaved either by heating or photochemical means, giving corresponding 1Ph-2R-1H-2,1-benzazaborolyl radicals (BabtBu)(.) and (Bab-Dipp)(.), which rapidly self-terminate. Nevertheless, their formation was unambiguously established by NMR analysis of the reaction mixtures containing products of the self-termination of the radicals after heating or irradiation. (Bab-Dipp)(.) radical was also characterized using EPR spectroscopy. Importantly, it turned out that the essentially non-polarized HC(sp(3))-C(sp(3))H bond in (Bab-tBu)(2) is also cleaved heterolytically with 2 equiv of MeLi, giving the mixture of Li+(SOL)(n)(Bab-tBu)(-) (SOL = THF or Et2O) and lithium methyl-substituted borate complex Li+(SOL)(n)(Bab-tBu-Me)(-) in a diastereoselective fashion.

Czech name

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Czech description

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Type

J_x - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)

CEP classification

CA - Inorganic chemistry

OECD FORD branch

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Project

<a href="/en/project/GAP207%2F12%2F0223" target="_blank" >GAP207/12/0223: Hybrid ligands for low valent metal centres stabilization/specific activation.</a><br>

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year

2016

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

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Volume of the periodical

22

Issue of the periodical within the volume

43

Country of publishing house

DE - GERMANY

Number of pages

10

Pages from-to

15340-15349

UT code for WoS article

000384807600018

EID of the result in the Scopus database

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