One‐Pot Cooperation of Single‐Atom Rh and Ru Solid Catalysts for a Selective Tandem Olefin Isomerization‐Hydrosilylation Process

Abstract

Realizing the full potential of oxide‐supported single‐atom metal catalysts (SACs) is key to successfully bridge the gap between the fields of homogeneous and heterogeneous catalysis. Here we show that the one‐pot combination of Ru1/CeO2 and Rh1/CeO2 SACs enables a highly selective olefin isomerization‐hydrosilylation tandem process, hitherto restricted to molecular catalysts in solution. Individually, monoatomic Ru and Rh sites show a remarkable reaction specificity for olefin double‐bond migration and anti‐Markovnikov α‐olefin hydrosilylation, respectively. First‐principles DFT calculations ascribe such selectivity to differences in the binding strength of the olefin substrate to the monoatomic metal centers. The single‐pot cooperation of the two SACs allows the production of terminal organosilane compounds with high regio‐selectivity (>95 %) even from industrially‐relevant complex mixtures of terminal and internal olefins, alongside a straightforward catalyst recycling and reuse. These results demonstrate the significance of oxide‐supported single‐atom metal catalysts in tandem catalytic reactions, which are central for the intensification of chemical processes.

Sustainable Synthesis of Bimetallic Single Atom Gold‐Based Catalysts with Enhanced Durability in Acetylene Hydrochlorination

“…Fitting of the extended X-ray absorption fine structure (EXAFS), using Au-C/O, Au-Cl and Au-Au/Pt contributions on the Au L 3 edge and Pt-C/O, Pt-Cl and Pt-Pt/Au on the Pt L 3 edge, revealed a decrease in the Au-Cl contribution in the order of Au-SA/C >Au-Pt/C > Au-NP/C (Figure 1c; Figure S3, Table S1, Supporting Information, coordination number, CN = 2.7 ± 0.3, ≈0.9, and 0.4 ± 0.1, respectively). Similar to the Au single atoms, also the Pt sites are surrounded by Cl neighboring atoms (Figure S4, Table S2, Supporting Information, CN = 2.6), suggesting that Cl ions are not removed during the synthesis of the catalyst, in line with previous literature reports [4,12] and corroborated by the surface and bulk chlorine contents derived from X-ray photoelectron spectroscopy (XPS) and elemental analysis, respectively (Table S3, Supporting Information). Besides metal-chloride contributions, the EXAFS fitting results for Au-Pt/C suggest further, the presence of metal-metal interactions (Table S1, Figure S3, Supporting Information).…”

Steric Effects in the Catalytic Tandem Isomerization‐Hydrosilylation Reaction

“…This limitation could be solved by a catalyst capable of tandem isomerization‐hydrosilylation of an internal alkene in which the previous isomerization from internal to terminal olefins and subsequent α‐olefin hydrosilylation is promoted by the same metal complex. Examples of efficient tandem isomerization‐hydrosilylation of internal alkenes catalysed by transition metals such as cobalt, [23–25] nickel, [26,27] iron, [28] rhodium [29] or ruthenium, [29] or even metal nanoparticles [30,31] have recently been reported. In most of these cases, large metal loadings or dual catalyst systems were necessary to achieve good results.…”

Recent Advances in Catalytic Hydrosilylations: Developments beyond Traditional Platinum Catalysts

“…DFT calculations ascribed the observed selectivity to differences in the binding strength of the alkene substrate where the single Ru atoms bind more strongly than the Rh counterparts. [95] 3.2. Non-Precious Metal Catalysts 3.2.1.…”