Evidence for the “cocktail” nature of platinum-catalyzed alkyne and alkene hydrosilylation reactions

Abstract

Evidence of the involvement of a “cocktail”-type catalytic system in the alkyne and alkene hydrosilylation reaction in the presence of platinum on a carbon support is reported.

PtII−N‐Heterocyclic Carbene Complexes in Solvent‐Free Alkene Hydrosilylation

“…Even though Pt colloids were not visibly detected in hydrosilylation mixtures when using Pt−NHC complexes as pre‐catalysts, [10a,g,i] the observed slow formation of Pt colloids in our case, when reacting 3 ae and 4 a stoichiometrically, indicates the possible “cocktail” nature of the studied catalytic system. This is similar to the recently described system by Ananikov and co‐workers, [12c] involving multiple platinum active species (both nanoclusters/nanoparticles and molecular complexes). Unfortunately, in the case of our neat protocol utilizing [Pt(IPr*)(DMS)Cl 2 ], the contribution of platinum colloidal species to the overall reaction mechanism has proven challenging to assess.…”

Designing Chemical Reaction Arrays Using Phactor and ChatGPT

“…We suspect the proposal to mix these compounds arises as an artifact of making a combinatorial array (phactor) out of the popular Pd complex and ligand choices from the literature (ChatGPT). Nonetheless, the observation that this “cocktail” of ligands was the most productive result could be supported by related reports of “cocktail” catalysis in the Buchwald–Hartwig coupling. − …”

Predicting 195Pt NMR Chemical Shifts in Water‐Soluble Inorganic/Organometallic Complexes with a Fast and Simple Protocol Combining Semiempirical Modeling and Machine Learning

“…[58][59][60][61][62][63][64][65] First established for Pd complexes in CÀ C- [66] and CÀ N-coupling reactions, [67] the phenomenon was found to take place in a Pt-catalyzed hydrosilylation reaction. [68][69][70][71][72] Fast automatic prediction of 195 Pt shifts with an empirical (ML) scheme could greatly simplify the reaction monitoring in the case of dynamic catalysis. Third, it is important to note that the number of water-soluble Pt complexes is somewhat limited despite their importance in medicinal chemistry and catalysis.…”

“…Qualitative changes in the nature of catalytic centers in the course of the reaction (dynamic catalysis) and the formation of a “cocktail” of catalytic centers often occur [58–65] . First established for Pd complexes in C−C‐ [66] and C−N‐coupling reactions, [67] the phenomenon was found to take place in a Pt‐catalyzed hydrosilylation reaction [68–72] . Fast automatic prediction of 195 Pt shifts with an empirical (ML) scheme could greatly simplify the reaction monitoring in the case of dynamic catalysis.…”