Closing the Organosilicon Synthetic Cycle: Efficient Heterogeneous Hydrosilylation of Alkenes over SiliaCatPt(0)

Abstract

A modest 0.5–1 mol % amount of the sol–gel entrapped hybrid catalyst SiliaCat Pt(0) selectively mediates the hydrosilylation of different olefins under Ar atmosphere at room temperature or at 65 °C, depending on the substrate. Low levels of Pt leaching ensure minimal amounts of platinum residues in crude product and no plant contamination. Valued platinum nanoparticles remain entrapped within the organosilica xerogel that can thus be reused.

Fifty Years of Hydrosilylation in Polymer Science: A Review of Current Trends of Low-Cost Transition-Metal and Metal-Free Catalysts, Non-Thermally Triggered Hydrosilylation Reactions, and Industrial Applications

“…Scale-up experiments from 2 to 100 mmol substrate indicate no loss of selectivity or conversion degree at higher amounts. [123] Polymers 2017, 9, 534 25 of 37 CO2 to generate silanols and formic acid in a one-pot reaction ( Figure 41) [120]. The high yield of up to 95% and TONs of 8100, however, are counterbalanced by the high prices of hydrosilanes.…”

“…Scale-up experiments from 2 to 100 mmol substrate indicate no loss of selectivity or conversion degree at higher amounts. [123] Other approaches to improve the durability of platinum-based catalysts and to further optimize the hydrosilylation process is the use of ionic liquids ILs as well as microreactors. Microreactors enable the performance of continuous chemical reaction process in tubes with small diameter, which results in higher yields due to a high surface:volume ratio and therefore increased mass transfer [124].…”

The Central Role of Chemistry in the Transition to the Solar Economy

“…6 This closes the organosilicon synthetic cycle, because the SiliaCat catalyst itself is made out of an alkyl-trialkoxysilane in its turn obtained via olefin hydrosilation. What is also relevant from a practical viewpoint is that the process scaled up 50 times retains both the high selectivity and conversion degree observed on the 2 mmol scale.…”

SiliaCat: A Versatile Catalyst Series for Synthetic Organic Chemistry

“…This industry, for example, has replaced with heterogeneously catalyzed methods many former stoichiometric processes used for the synthesis of vitamins, carotenoids, flavoring and fragrance compounds. 7 Along with the latter new catalysts, the SiliaCat (a trademark of SiliCycle) sol-gel nanostructured hybrid silicas immobilizing and stabilizing organocatalytic species and unstable metal nanoparticles have emerged as a versatile nanochemistry technology applicable to a large variety of reactions of direct relevance to the manufacture of fine chemicals and APIs, including alcohol selective oxidation, 8 hydrogenation of nitroarenes, 9 fully stereoselective hydrogenation of vegetable oils, 10 carbon-carbon bond formation, 11 ultraselective hydrosilylation 12 and hydrogenation of olefins. 13 We have explained elsewhere [14][15] how their successful application derives from the deliberate chemical design of the right hybrid nanostructures.…”