Expanding the Role of Dimeric Species: On-Cycle Involvement, Improved Stability, and Control of Stereo-Specificity. A Case Study of Atom-Economic Catalytic Hydrothiolation

Expanding the Role of Dimeric Species: On-Cycle Involvement, Improved Stability, and Control of Stereo-Specificity. A Case Study of Atom-Economic Catalytic Hydrothiolation Full article

Journal

ACS Catalysis
ISSN: 2155-5435

Output data

Year: 2023, Volume: 13, Number: 6, Pages: 3591-3604 Pages count : 14 DOI: 10.1021/acscatal.2c06406

Authors

Sahharova Liliya T. ¹ , Burykina Julia V. ¹ , Kostyukovich Alexander Yu. ¹ , Eremin Dmitry B. ² , Boiko Daniil A. ¹ , Fakhrutdinov Artem N. ¹ , Ananikov Valentine P. ¹

Affiliations

1	Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, Moscow 119991, Russia
2	The Bridge@USC, University of Southern California, 1002 Childs Way, Los Angeles, California 90089-3502, United States

A common assumption that dimeric metal complexes in many catalytic systems represent a resting state and are not directly involved in catalytic processes was revised in a combined experimental and theoretical study. On-cycle participation of dimeric metal complexes, rather than typically assumed off-cycle involvement, was revealed, and advantageous performance in terms of improved selectivity was observed. The conceptual rationalization for the participation of dimeric species in the catalytic cycle was developed. The Pd-catalyzed hydrothiolation process (where strong Pd–S binding is well established and a persistent opinion for the inactive/poisoning role of dimeric species is presumed) was evaluated as a challenging system to test the concept. Activation of an (NHC)Pd(Cl)(acac) precatalyst (NHC─N-heterocyclic carbene and acac─acetylacetonate) under the reaction conditions produced monomeric (NHC)Pd(SPh)2 or dimeric (NHC)2Pd2(SPh)4 species depending on the steric bulkiness of the NHC ligand. Dimeric complexes possessed higher selectivity and tolerated disulfide impurities in contrast to monomeric complexes. Quantum chemical modeling suggested that dimeric catalysis proceeds through the opening of only one (μ-SPh)–Pd bridging bond with retention of the dimeric structure. The second bridging bond is maintained, which prevents the monomerization of the complex. Catalytically active species were detected in a hydrothiolation reaction by high-resolution mass spectrometry and NMR spectroscopy. Proving the opportunity for productive homogeneous catalysis via strongly coordinated dimeric metal species opens new opportunities for catalyst design in the increased nuclearity dimension.

Sahharova L.T. , Burykina J.V. , Kostyukovich A.Y. , Eremin D.B. , Boiko D.A. , Fakhrutdinov A.N. , Ananikov V.P.
Expanding the Role of Dimeric Species: On-Cycle Involvement, Improved Stability, and Control of Stereo-Specificity. A Case Study of Atom-Economic Catalytic Hydrothiolation
ACS Catalysis. 2023. V.13. N6. P.3591-3604. DOI: 10.1021/acscatal.2c06406 WOS Scopus OpenAlex

Web of science:	WOS:000954938900001
Scopus:	2-s2.0-85149147156
OpenAlex:	W4322492210

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OpenAlex	3
Web of science	4
Scopus	3