Fast and Slow Release of Catalytically Active Species in Metal/NHC Systems Induced by Aliphatic Amines

The behavior of ubiquitously used nickel, palladium, and platinum complexes containing N-heterocyclic carbene ligands was studied in solution in the presence of aliphatic amines. Transformation of M(NHC)X2L complexes readily occurred according to the following reactions: (i) release of the NHC ligand in the form of azolium salt and formation of metal clusters or nanoparticles and (ii) isomerization of mono-NHC complexes M(NHC)X2L to bis-NHC derivatives M(NHC)2X2. Facile cleavage of the M-NHC bond was observed and provided the possibility for fast release of catalytically active NHC-free metal species. Bis-NHC metal complexes M(NHC)2X2 were found to be significantly more stable and represented a molecular reservoir of catalytically active species. Slow decomposition of the bis-NHC complexes by removal of the NHC ligands (also in the form of azolium salts) occurred, generating metal clusters or nanoparticles. The observed combination of dual fast- and slow-release channels is an intrinsic latent opportunity of M/NHC complexes, which balances the activity and durability of a catalytic system. The fast release of catalytically active species from M(NHC)X2L complexes can rapidly initiate catalytic transformation, while the slow release of catalytically active species from M(NHC)2X2 complexes can compensate for degradation of catalytically active species and help to maintain a reliable amount of catalyst. The study clearly shows an outstanding potential of dynamic catalytic systems, where the key roles are played by the lability of the M-NHC framework rather than its stability. © 2018 American Chemical Society.

Khazipov O.V.1 , Shevchenko M.A.1 , Chernenko A.Y.1 , Astakhov A.V.1 , Pasyukov D.V.1 , Eremin D.B.2 , Zubavichus Y.V.3 , Khrustalev V.N. 3, 4 , Chernyshev V.M.1 , Ananikov V.P.1, 2
American Chemical Society
Номер выпуска
  • 1 Platov South-Russian State Polytechnic University (NPI), Prosveschenya 132, Novocherkassk, 346428, Russian Federation
  • 2 Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, Moscow, 119991, Russian Federation
  • 3 National Research Center, Kurchatov Institute, Acad. Kurchatov Sq. 1, Moscow, 123182, Russian Federation
  • 4 Peoples' Friendship University of Russia, Miklukho-Maklay St. 6, Moscow, 117198, Russian Federation
Ключевые слова
Amines; Ligands; Metal complexes; Metal nanoparticles; Metals; Platinum compounds; Aliphatic amines; Catalytic system; Catalytic transformation; Catalytically active species; Metal cluster; N-heterocyclic carbene ligands; NHC-metal complex; Platinum complexes; Palladium compounds
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