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Dehydrogenation of amine–boranes catalyzed by a \( \mathrm{PC}_{sp^3}\mathrm{P} \) pincer iridium complex

Vladislava Aleksandrovna Kirkina 1
Vladislava Aleksandrovna Kirkina
, 
Elena Sergeevna Osipova 1
Elena Sergeevna Osipova
,  , 
Gleb Aleksandrovich Silantyev 1
Gleb Aleksandrovich Silantyev
, 
Dmitri Gelman 2
Dmitri Gelman
,  , 
Natalia Viktorovna Belkova 1
Natalia Viktorovna Belkova
10.1016/j.mencom.2020.05.004
Published 2020-04-30
Communication , Volume 30, Issue 3, 276-278
6
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Kirkina V. A. et al. Dehydrogenation of amine–boranes catalyzed by a \( \mathrm{PC}_{sp^3}\mathrm{P} \) pincer iridium complex // Mendeleev Communications. 2020. Vol. 30. No. 3. pp. 276-278.
GOST all authors (up to 50) Copy
Kirkina V. A., Osipova E. S., Filippov O. A., Silantyev G. A., Gelman D., Shubina E. S., Belkova N. V. Dehydrogenation of amine–boranes catalyzed by a \( \mathrm{PC}_{sp^3}\mathrm{P} \) pincer iridium complex // Mendeleev Communications. 2020. Vol. 30. No. 3. pp. 276-278.
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TY - JOUR
DO - 10.1016/j.mencom.2020.05.004
UR - https://mendcomm.colab.ws/publications/10.1016/j.mencom.2020.05.004
TI - Dehydrogenation of amine–boranes catalyzed by a \( \mathrm{PC}_{sp^3}\mathrm{P} \) pincer iridium complex
T2 - Mendeleev Communications
AU - Kirkina, Vladislava Aleksandrovna
AU - Osipova, Elena Sergeevna
AU - Filippov, Oleg Andreevich
AU - Silantyev, Gleb Aleksandrovich
AU - Gelman, Dmitri
AU - Shubina, Elena Solomonovna
AU - Belkova, Natalia Viktorovna
PY - 2020
DA - 2020/04/30
PB - Mendeleev Communications
SP - 276-278
IS - 3
VL - 30
ER -
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@article{2020_Kirkina,
author = {Vladislava Aleksandrovna Kirkina and Elena Sergeevna Osipova and Oleg Andreevich Filippov and Gleb Aleksandrovich Silantyev and Dmitri Gelman and Elena Solomonovna Shubina and Natalia Viktorovna Belkova},
title = {Dehydrogenation of amine–boranes catalyzed by a \( \mathrm{PC}_{sp^3}\mathrm{P} \) pincer iridium complex},
journal = {Mendeleev Communications},
year = {2020},
volume = {30},
publisher = {Mendeleev Communications},
month = {Apr},
url = {https://mendcomm.colab.ws/publications/10.1016/j.mencom.2020.05.004},
number = {3},
pages = {276--278},
doi = {10.1016/j.mencom.2020.05.004}
}
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Kirkina, Vladislava Aleksandrovna, et al. “Dehydrogenation of amine–boranes catalyzed by a \( \mathrm{PC}_{sp^3}\mathrm{P} \) pincer iridium complex.” Mendeleev Communications, vol. 30, no. 3, Apr. 2020, pp. 276-278. https://mendcomm.colab.ws/publications/10.1016/j.mencom.2020.05.004.
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Keywords

amine--boranes
catalytic dehydrogenation
DFT calculations
iridium pincer complexes
molecular spectroscopy

Abstract

Dibenzobarrelene-based \( \mathrm{PC}_{sp^3}\mathrm{P} \) pincer iridium complex bearing dangling CH2OH groups, \( (\mathrm{PC}_{sp^3}\mathrm{P^{CH_{2}OH}})\mathrm{IrH(Cl)} \), catalyzes the dehydrogenation of amine-boranes at the reaction rate changing counter intuitively in the order: \( \mathrm{Me_2NH \cdot BH_3 > Bu^t NH_2 \cdot BH_3 > NH_3 \cdot BH_3} \). The spectral (IR and NMR) data and DFT/M06 calculations have revealed that the binding of amine-boranes to the dangling OH group leads to an additional stabilization of the Ir···OH bond, thus hampering the dehydrogenation reaction, whereas the amine-borane coordination to iridium entails a fac- to mer-transformation of the complex and initiates the catalytic H2 evolution.

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