@article{e8c2fbb6b3bf4a26b2b3b071918ef284,
title = "Tunable Latency of Hydrosilylation Catalyst by Ligand Density on Nanoparticle Supports",
abstract = "Functionalizing inorganic particles with organic ligands is a common technique for heterogenizing organometallic catalysts. We describe how coordinating molecular platinum to silica nanoparticles functionalized with a high density of norbornene ligands causes unexpected latency of the catalytic activity in hydrosilylation reactions when compared to an identical reaction in which the norbornene is not tethered (2 % vs 97 % conversion in 1 h). Performing the hydrosilylation at elevated temperature (70 °C) suppresses this activity delay, suggesting the usefulness of this technique towards temperature-triggered catalysis. We demonstrate that this latency is related to ligand density on the particle surface, chemical structure of the norbornene, and silica nanoparticle topology. We also establish the benefit of this latency for triggered curing of silicone elastomers. Overall, our work establishes the non-innocent role of inorganic supports when functionalized with organometallic complexes.",
keywords = "Homogeneous Catalysis, Hydrosilylation, Immobilized Catalyst, Latency, Silicon Chemistry",
author = "Miller, {Susannah A.} and Damien Guironnet",
note = "The authors would like to thank Drs. Matt Jeletic, Dimi Katsoulis, and Jon Degroot of Dow Performance Silicones for helpful discussions. The authors would also like to acknowledge Dow for supplying MD'M, MviD130Mvi, and MD93D{\textquoteright}6M siloxanes. The authors would also like to thank Dr. Ben Suslick for performing the differential scanning calorimetry measurements. This research was carried out in part in the Materials Research Laboratory Central Research Facilities, University of Illinois. ICP-MS was performed by the Microanalysis Laboratory at the University of Illinois. This work was funded by Dow Chemical Company. The authors would like to thank Drs. Matt Jeletic, Dimi Katsoulis, and Jon Degroot of Dow Performance Silicones for helpful discussions. The authors would also like to acknowledge Dow for supplying MD'M, MDM, and MDD{\textquoteright}M siloxanes. The authors would also like to thank Dr. Ben Suslick for performing the differential scanning calorimetry measurements. This research was carried out in part in the Materials Research Laboratory Central Research Facilities, University of Illinois. ICP‐MS was performed by the Microanalysis Laboratory at the University of Illinois. This work was funded by Dow Chemical Company. vi 130 vi 93 6",
year = "2023",
month = jan,
day = "26",
doi = "10.1002/anie.202214267",
language = "English (US)",
volume = "62",
journal = "Angewandte Chemie - International Edition",
issn = "1433-7851",
publisher = "John Wiley & Sons, Ltd.",
number = "5",
}