ABSTRACT
Herein, we report the catalytic activity of a series of platinum(II) pre-catalysts, bearing N-heterocyclic carbene (NHC) ligands, in the alkene hydrosilylation reaction. Their structural and electronic properties are fully investigated using X-ray diffraction analysis and nuclear magnetic resonance spectroscopy (NMR). Next, our study presents a structure-activity relationship within this group of pre-catalysts and gives mechanistic insights into the catalyst activation step. An exceptional catalytic performance of one of the complexes is observed, reaching a turnover number (TON) of 970 000 and a turnover frequency (TOF) of 40 417â h-1 at 1â ppm catalyst loading. Finally, an attractive solvent-free and open-to-air alkene hydrosilylation protocol, featuring efficient platinum removal (reduction of residual Pt from 582â ppm to 5.8â ppm), is disclosed.
ABSTRACT
The integration of a membrane separation protocol with the platinum-catalyzed hydrosilylation of olefins is investigated. The catalytic reaction is first optimized in batch where [Pt(IPr*)(dms)Cl2 ] (IPr*=1,3-bis[2,6-bis(diphenylmethyl)-4-methylphenyl]imidazol-2-ylidene, dms=dimethyl sulfide) demonstrates superior activity compared to the less sterically encumbered [Pt(SIPr)(dms)Cl2 ] (SIPr=1,3-bis(2,6-diisopropylphenyl)imidazolidine) congener. Filtration conditions are identified in membrane screening experiments. Hydrosilylation of 1-octene catalyzed by [Pt(IPr*)(dms)Cl2 ] is conducted in continuous mode and the platinum catalyst is separated efficiently over the commercially available Borsig oNF-2 membrane, all under solvent-free conditions. An advantage of this process is that both reaction and separation are coupled in a single step. Moreover, at the end of the process the intact catalyst was recovered in 80 % yield as an off-white solid without any further purification.
