We report the first example of successful heterogenization of the classical PdI(4)(2-)carbonylation catalyst, achieved in two simple steps from ionic liquid-functionalized multi-walled carbon nanotubes (MWCNTs). The newly developed materials (PdI4@MWCNT-imi-X, X = Br, I) present the PdI(4)(2-)anion sup-ported on an imidazolium network (imi) grown on MWCNTs and have been fully characterized. The activity of PdI4@MWCNT-imi-X has been successfully tested in a paradigmatic carbonylation reac-tion, the oxidative monoaminocarbonylation of 1-alkynes with amines to give high value added 2-ynamides (obtained in good yields, 50-84%, starting from various substrates). The heterogeneous catalyst could be easily recycled and showed a good efficiency even after the fourth recycle, when deactivation began to occur owing to the formation of inactive Pd(0) species, as confirmed by XPS analysis. Hot and cold filtration tests were compatible with an essentially heterogeneous catalytic process, and limited metal contamination in the final organic compounds occurred, as assessed by ICP-MS analysis of repre-sentative carbonylation products.(C) 2022 Elsevier Inc. All rights reserved.
Heterogenizing palladium tetraiodide catalyst for carbonylation reactions / Ziccarelli, I.; Mancuso, R.; Giacalone, F.; Calabrese, C.; La Parola, V.; De Salvo, A.; Della Ca', N.; Gruttadauria, M.; Gabriele, B.. - In: JOURNAL OF CATALYSIS. - ISSN 1090-2694. - 413:(2022), pp. 1098-1110. [10.1016/j.jcat.2022.08.007]
Heterogenizing palladium tetraiodide catalyst for carbonylation reactions
Della Ca' N.;
2022-01-01
Abstract
We report the first example of successful heterogenization of the classical PdI(4)(2-)carbonylation catalyst, achieved in two simple steps from ionic liquid-functionalized multi-walled carbon nanotubes (MWCNTs). The newly developed materials (PdI4@MWCNT-imi-X, X = Br, I) present the PdI(4)(2-)anion sup-ported on an imidazolium network (imi) grown on MWCNTs and have been fully characterized. The activity of PdI4@MWCNT-imi-X has been successfully tested in a paradigmatic carbonylation reac-tion, the oxidative monoaminocarbonylation of 1-alkynes with amines to give high value added 2-ynamides (obtained in good yields, 50-84%, starting from various substrates). The heterogeneous catalyst could be easily recycled and showed a good efficiency even after the fourth recycle, when deactivation began to occur owing to the formation of inactive Pd(0) species, as confirmed by XPS analysis. Hot and cold filtration tests were compatible with an essentially heterogeneous catalytic process, and limited metal contamination in the final organic compounds occurred, as assessed by ICP-MS analysis of repre-sentative carbonylation products.(C) 2022 Elsevier Inc. All rights reserved.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
