Dehydrogenation of amine–boranes catalyzed by a PCsp3P pincer iridium complex

Vladislava A. Kirkina; Elena S. Osipova; Oleg A. Filippov; Gleb A. Silantyev; Dmitri Gelman; Elena S. Shubina; Natalia V. Belkova

doi:10.1016/j.mencom.2020.05.004

Dehydrogenation of amine–boranes catalyzed by a PC_sp³P pincer iridium complex

Vladislava A. Kirkina, Elena S. Osipova, Oleg A. Filippov, Gleb A. Silantyev, Dmitri Gelman, Elena S. Shubina, Natalia V. Belkova^*

^*Corresponding author for this work

Institute of Chemistry

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

Abstract

Dibenzobarrelene-based PC_sp³P pincer iridium complex bearing dangling CH₂OH groups, ((PC_sp³P^CH₂OH)IrH(Cl), catalyzes the dehydrogenation of amine–boranes at the reaction rate changing counter intuitively in the order: Me₂NH·BH₃ > > Bu^tNH₂·BH₃ > NH₃·BH₃. 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.

Original language	English
Pages (from-to)	276-278
Number of pages	3
Journal	Mendeleev Communications
Volume	30
Issue number	3
DOIs	https://doi.org/10.1016/j.mencom.2020.05.004
State	Published - 1 May 2020

Bibliographical note

Publisher Copyright:
© 2020

Keywords

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

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10.1016/j.mencom.2020.05.004

Cite this

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title = "Dehydrogenation of amine–boranes catalyzed by a PCsp3P pincer iridium complex",

abstract = "Dibenzobarrelene-based PCsp3P pincer iridium complex bearing dangling CH2OH groups, ((PCsp3PCH2OH)IrH(Cl), catalyzes the dehydrogenation of amine–boranes at the reaction rate changing counter intuitively in the order: Me2NH·BH3 > > ButNH2·BH3 > NH3·BH3. 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.",

keywords = "DFT calculations, amine–boranes, catalytic dehydrogenation, iridium pincer complexes, molecular spectroscopy",

author = "Kirkina, {Vladislava A.} and Osipova, {Elena S.} and Filippov, {Oleg A.} and Silantyev, {Gleb A.} and Dmitri Gelman and Shubina, {Elena S.} and Belkova, {Natalia V.}",

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year = "2020",

month = may,

day = "1",

doi = "10.1016/j.mencom.2020.05.004",

language = "אנגלית",

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T1 - Dehydrogenation of amine–boranes catalyzed by a PCsp3P pincer iridium complex

AU - Kirkina, Vladislava A.

AU - Osipova, Elena S.

AU - Filippov, Oleg A.

AU - Silantyev, Gleb A.

AU - Gelman, Dmitri

AU - Shubina, Elena S.

AU - Belkova, Natalia V.

PY - 2020/5/1

Y1 - 2020/5/1

N2 - Dibenzobarrelene-based PCsp3P pincer iridium complex bearing dangling CH2OH groups, ((PCsp3PCH2OH)IrH(Cl), catalyzes the dehydrogenation of amine–boranes at the reaction rate changing counter intuitively in the order: Me2NH·BH3 > > ButNH2·BH3 > NH3·BH3. 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.

AB - Dibenzobarrelene-based PCsp3P pincer iridium complex bearing dangling CH2OH groups, ((PCsp3PCH2OH)IrH(Cl), catalyzes the dehydrogenation of amine–boranes at the reaction rate changing counter intuitively in the order: Me2NH·BH3 > > ButNH2·BH3 > NH3·BH3. 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.

KW - DFT calculations

KW - amine–boranes

KW - catalytic dehydrogenation

KW - iridium pincer complexes

KW - molecular spectroscopy

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