Aluminium porphyrins catalyse the hydrogenation of CO2 with H2

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F24%3A10488903" target="_blank" >RIV/00216208:11310/24:10488903 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=eP4FwsJ501" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=eP4FwsJ501</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d4sc03665d" target="_blank" >10.1039/d4sc03665d</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Aluminium porphyrins catalyse the hydrogenation of CO2 with H2

Popis výsledku v původním jazyce

Boron-based frustrated Lewis pairs (FLPs) have become well-established catalysts for the hydrogenation of a wide range of functional groups. Conversely, aluminium-based FLP hydrogenation catalysts are less common, especially for CO2 reduction. They are mostly confined to the hydrogenation of imines, alkenes, and alkynes even though aluminium is much more abundant than boron and forms structurally related compounds. Moreover, aluminium forms penta- and hexa-coordinated complexes, which remain untested in FLP hydrogenation catalysis. Herein, we demonstrate that cationic, hexa-coordinated diaqua-meso-tetraphenylporphyrin aluminium complexes [Al(TPP)(OH2)2]X and [Al(tBuTPP)(OH2)2]X (X = Cl(-), OTf(-), ClO4(-)) form FLPs with nitrogen bases, activate H2, and reductively couple CO2 to amines, yielding N-formylamines and water. Our experimental results and DFT analysis indicate that H2 activation involves the formation of an FLP, base-promoted CO2 reduction and formate salt elimination from the FLP, as proposed for transition metal-catalyzed N-formylations. These similarities in the reaction mechanism and structure of aluminium complexes brings Al-based FLPs closer to transition metal catalysis and may enable us to apply this knowledge to ligand design to enhance main group metal-promoted hydrogenations.

Název v anglickém jazyce

Aluminium porphyrins catalyse the hydrogenation of CO2 with H2

Popis výsledku anglicky

Boron-based frustrated Lewis pairs (FLPs) have become well-established catalysts for the hydrogenation of a wide range of functional groups. Conversely, aluminium-based FLP hydrogenation catalysts are less common, especially for CO2 reduction. They are mostly confined to the hydrogenation of imines, alkenes, and alkynes even though aluminium is much more abundant than boron and forms structurally related compounds. Moreover, aluminium forms penta- and hexa-coordinated complexes, which remain untested in FLP hydrogenation catalysis. Herein, we demonstrate that cationic, hexa-coordinated diaqua-meso-tetraphenylporphyrin aluminium complexes [Al(TPP)(OH2)2]X and [Al(tBuTPP)(OH2)2]X (X = Cl(-), OTf(-), ClO4(-)) form FLPs with nitrogen bases, activate H2, and reductively couple CO2 to amines, yielding N-formylamines and water. Our experimental results and DFT analysis indicate that H2 activation involves the formation of an FLP, base-promoted CO2 reduction and formate salt elimination from the FLP, as proposed for transition metal-catalyzed N-formylations. These similarities in the reaction mechanism and structure of aluminium complexes brings Al-based FLPs closer to transition metal catalysis and may enable us to apply this knowledge to ligand design to enhance main group metal-promoted hydrogenations.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/GM21-27431M" target="_blank" >GM21-27431M: Lewisovy kyseliny a frustrované Lewisovy páry pro redukčně kondenzační reakce oxidu uhličitého s aminy</a><br>

Návaznosti

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

Rok uplatnění

2024

Kód důvěrnosti údajů

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

Název periodika

Chemical Science

ISSN

2041-6520

e-ISSN

2041-6539

Svazek periodika

15

Číslo periodika v rámci svazku

48

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

9

Strana od-do

20573-20581

Kód UT WoS článku

001362169800001

EID výsledku v databázi Scopus

2-s2.0-85210315231