Alkene hydrosilylation catalyzed by easily assembled Ni(ii)-carboxylate MOFs

Abstract

Easily-assembled Ni MOFs are efficient and robust catalysts for alkene hydrosilylation.

Developing a Highly Active Catalytic System Based on Cobalt Nanoparticles for Terminal and Internal Alkene Hydrosilylation

“…Taking advantage of such results, we decided to study the possibility to transform otherwise inactive internal alkenes into anti-Markovnikov hydrosilylation products through the tandem isomerization–hydrosilylation reaction. Currently, there are only few examples reporting non-noble metal systems capable of performing the tandem isomerization–hydrosilylation of internal hexenes or octenes with pentamethyldisiloxane, (MeO) 3 SiH, (EtO) 3 SiH, Et 2 SiH 2 , Ph 2 SiH 2 , and PhSiH 3 in 61–97% yields. ,,,− The present Co-4 catalyst was first tested in the hydrosilylation of 2- trans -octene, 1-methyl-1-cyclohexene, and methyl oleate under standard thermal conditions at 30 °C, but no hydrosilylated products were detected. However, when the samples were left under UV irradiation (λ > 250 nm), the efficient isomerization of the internal CC bond occurred, giving rise to the terminal alkylsilane products (Scheme ).…”

“…An important alternative to homogeneous non-precious metal catalysts in alkene hydrosilylation is to develop analogous heterogeneous systems, which in recent years has gained momentum. Current examples of heterogeneous non-precious metal catalysts capable of alkene hydrosilylation have been prepared as supported catalysts, − by incorporating metals into metal–organic frameworks or layers and as dispersed nanoparticles (NPs) onto supports . While the latter examples boast at times with large alkene scopes, they are currently limited by the choice of the silane counterpart, which, in most cases, involves the use of activated silanes (PhSiH 3 and Ph 2 SiH 2 ) that are not relevant for industrial applications.…”

iO₂-Supported Single-Atom Catalysts for Photocatalytic Reactions

“…H2 evolution by photocatalysis is the most low-cost method to produce green hydrogen 113 , green hydrogen is the hydrogen generated in a green chemical process. Abundant metal oxides with tunable bandgap are ideal models to be employed to fabricate the catalysts [114][115][116] . Considering the promotional effect of noble metals to the reaction rate, the metal oxides are usually decorated with noble metals to reach a plausible hydrogen generation rate.…”

Recent Advances in Catalytic Hydrosilylations: Developments beyond Traditional Platinum Catalysts

“…The single metal sites are considered to be stabilized by the hydroxyl groups from the MOF forming the active centers. Using this catalyst, the hydrosilylation of n ‐octene and diphenylsilane was carried out on a 150 mmol scale under mild conditions with high conversion and selectivity [98] . Furthermore, isolated Ni centers stabilized by heterogeneous ligands have been applied for hydrosilylation reactions very recently.…”

“…[97] In 2019, an ovel supported nickel catalyst was prepared whereby isolated nickel centers were anchored on am etalorganic framework (MOF) carrier.T he single metal sites are considered to be stabilized by the hydroxyl groups from the MOF forming the active centers.U sing this catalyst, the hydrosilylation of n-octene and diphenylsilane was carried out on a1 50 mmol scale under mild conditions with high conversion and selectivity. [98] Furthermore,isolated Ni centers stabilized by heterogeneous ligands have been applied for hydrosilylation reactions very recently.I nt his latter case, ap orous organic polymer containing Xantphos (POP-Xantphos) moieties was used to stabilize the isolated nickel centers.T he prepared Ni-POP-Xantphos catalyst demonstrated high regio-and stereoselectivity in the hydrosilylation of alkynes.T he obtained selectivity was considered to be controlled by the microporous structure of POP-Xantphos. [99] [93] Copyright2 018, American Chemical Society.…”