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

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

Журнал

Organometallics
ISSN: 0276-7333 , E-ISSN: 1520-6041

Вых. Данные

Год: 2018, Том: 37, Номер: 9, Страницы: 1483-1492 Страниц : 10 DOI: 10.1021/acs.organomet.8b00124

Авторы

Khazipov Oleg V. ¹ , Shevchenko Maxim A. ¹ , Chernenko Andrey Yu. ¹ , Astakhov Alexander V. ¹ , Pasyukov Dmitry V. ¹ , Eremin Dmitry B. ² , Zubavichus Yan V. ³ , Khrustalev Victor N. ^3,4 , Chernyshev Victor M. ¹ , Ananikov Valentine P. ^1,2

Организации

1	Platov South-Russian State Polytechnic University (NPI)
2	N.D. Zelinsky Institute of Organic Chemistry RAS
3	National Research Centre "Kurchatov Institute"
4	Peoples’ Friendship University of Russia (RUDN University)

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.

Khazipov O.V. , Shevchenko M.A. , Chernenko A.Y. , Astakhov A.V. , Pasyukov D.V. , Eremin D.B. , Zubavichus Y.V. , Khrustalev V.N. , Chernyshev V.M. , Ananikov V.P.
Fast and Slow Release of Catalytically Active Species in Metal/NHC Systems Induced by Aliphatic Amines
Organometallics. 2018. V.37. N9. P.1483-1492. DOI: 10.1021/acs.organomet.8b00124 Scopus OpenAlex

Scopus:	2-s2.0-85046965332
OpenAlex:	W2801561655

БД	Цитирований
OpenAlex	47