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

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CA - Anorganická chemie

OECD FORD obor

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Projekt

<a href="/cs/project/GAP207%2F12%2F0223" target="_blank" >GAP207/12/0223: Hybridní ligandy pro stabilizaci/specifickou aktivaci kovových center v nízkých oxidačních stavech.</a><br>

Návaznosti

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

Rok uplatnění

2016

Kód důvěrnosti údajů

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

Název periodika

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

—

Svazek periodika

22

Číslo periodika v rámci svazku

43

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

10

Strana od-do

15340-15349

Kód UT WoS článku

000384807600018

EID výsledku v databázi Scopus

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