Carbon dioxide reduction by an AlOP frustrated Lewis pair
The reaction of t Bu 2 P(O)H with Bis 2 AlH (Bis = CH(SiMe 3 ) 2 ) afforded the adduct t Bu 2 P(H)OAl(H)Bis 2 ( 3 ). It slowly releases H 2 to form the first oxygen-bridged geminal Al/P frustrated Lewis pair t Bu 2 POAlBis 2 . It is capable of reversibly binding molecular hydrogen to afford 3 , show...
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| Published in | Chemical science (Cambridge) Vol. 13; no. 27; pp. 888 - 894 |
|---|---|
| Main Authors | , , , , , , , |
| Format | Journal Article |
| Published |
13.07.2022
|
| Online Access | Get full text |
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| Summary: | The reaction of
t
Bu
2
P(O)H with Bis
2
AlH (Bis = CH(SiMe
3
)
2
) afforded the adduct
t
Bu
2
P(H)OAl(H)Bis
2
(
3
). It slowly releases H
2
to form the first oxygen-bridged geminal Al/P frustrated Lewis pair
t
Bu
2
POAlBis
2
. It is capable of reversibly binding molecular hydrogen to afford
3
, shown by NMR and H/D scrambling experiments, and forms a 1,2-adduct with CO
2
. Importantly, the H
2
adduct
3
reduces CO
2
in a stoichiometric reaction leading to the formic acid adduct
t
Bu
2
P(H)OAl(CO
2
H)Bis
2
. The formation of the different species was explored by density functional theory calculations which provide support for the experimental results. All products were characterized by NMR spectroscopy as well as X-ray diffraction experiments and elemental analyses.
Addition
vs.
reduction: the geminal FLP Bis
2
AlOPtBu
2
can reversibly bind molecular hydrogen, it reacts with CO
2
to give an adduct, and its hydrogen adduct reduces CO
2
to an adduct of formic acid. |
|---|---|
| Bibliography: | Electronic supplementary information (ESI) available: NMR spectra, crystallographic data and computational details. CCDC For ESI and crystallographic data in CIF or other electronic format see 21519062151909 https://doi.org/10.1039/d2sc01870e |
| ISSN: | 2041-6520 2041-6539 |
| DOI: | 10.1039/d2sc01870e |