Volume 244, 2023

Effect of liquid confinement on regioselectivity in the hydrosilylation of alkynes with cationic Rh(i) N-heterocyclic carbene catalysts

Abstract

Polymeric mesoporous monoliths were prepared via ring-opening metathesis polymerization (ROMP) from norbornene (NBE), 1,4,4a,5,8,8a-hexahydro-1,4,5,8-exo,endo-dimethanonaphthalene (DMN-H6), tris(norborn-2-enylmethylenoxy)methylsilane and the 1st-generation Grubbs catalyst [RuCl2(PCy3)2(CHC6H5)] in the presence of 2-propanol and toluene and surface grafted with 1-(2-((norborn-5-ene-2-carbonyl)oxy)ethyl)-3-ethyl-1H-imidazol-3-ium tetrafluoroborate. Subsequently, a supported ionic-liquid-phase (SILP) system was created by immobilizing the ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4] with the cationic catalyst [Rh((1-pyrid-1-yl)-3-mesitylimidazol-2-ylidene)(COD)+BF4] (Rh-1; COD = 1,4-cyclooctadiene) dissolved therein. The regio- and stereoselectivity of Rh-1 dissolved in the IL and supported on the mesoporous monolith, referred to as Rh@SILPROMP, in the hydrosilylation of 1-alkynes with HSiMe2Ph was studied and compared to that of the homogeneous catalyst Rh-1 under biphasic conditions using methyl tert-butyl ether (MTBE) as a second organic phase. Different amounts of IL were used, which allowed for the creation of SILPs with different layer thicknesses. Rh@SILPROMP provided by far better β-(Z) selectivity for both aromatic and aliphatic 1-alkynes in comparison to Rh-1 used under biphasic conditions. The highest β-(Z) selectivity was obtained with the thinnest IL layer. No leaching of the IL or rhodium from the SILP system into the organic phase was observed, resulting in virtually metal-free hydrosilylation products. The data obtained with Rh@SILPROMP were also compared with those from previous studies with Rh-1 in the same IL supported on polyurethane-derived mesoporous monolithic supports (Rh@SILPPUR) and on mesoporous SBA-15 (Rh@SILPSBA-15). For the first time, the use of a liquid confinement created by both a SILP and the support itself to tune the transition state of an organometallic catalyst by non-covalent interactions and thus stereo- and regioselectivity is outlined.

Graphical abstract: Effect of liquid confinement on regioselectivity in the hydrosilylation of alkynes with cationic Rh(i) N-heterocyclic carbene catalysts

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
14 nov. 2022
Accepted
22 déc. 2022
First published
22 déc. 2022

Faraday Discuss., 2023,244, 39-50

Effect of liquid confinement on regioselectivity in the hydrosilylation of alkynes with cationic Rh(I) N-heterocyclic carbene catalysts

P. K. R. Panyam and M. R. Buchmeiser, Faraday Discuss., 2023, 244, 39 DOI: 10.1039/D2FD00152G

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