Addition, substitution, and telomerization reactions of olefins in the presence of metal carbonyls or colloidal iron

Computational insights into the mechanism of iron carbonyl-catalyzed ethylene hydrosilylation or dehydrogenative silylation

“…predicted to be favorable since Fe(CO) 3 (H) 2 (g 2 -C 2 H 4 ) 8b 2 is less stable than Fe(CO) 4 (g 2 -C 2 H 3 SiMe 3 ) 8b 1 (7.65 vs À6.39 kcal/mol). It shows that side product ethane will not be afforded, which is consistent with the experiments without alkane observed under thermal conditions [20]. Whereas at the condition of irradiation, process 7b 1 ?…”

“…The earliest report on the selective formation of vinylsilanes was obtained by the Fe(CO) 5 -catalyzed reaction of olefins with HSiEt 3 under the stringent thermal conditions (100-140°C) [20], and their experiments showed that an excess of silicon hydride (R' 3 SiH) favored the silylated alkane (A), whereas an excess of olefin favored the unsaturated vinylsilane (B). However, efforts to detect the intermediates had been hindered by the hermetically sealed reaction conditions.…”

Iron‐Catalysed Hydrofunctionalisation of Alkenes and Alkynes

“…The iron-catalysed hydrosilylation of alkenes was first achieved by using iron pentacarbonyl (Scheme 30). [75] Good to excellent conversions of silane were obtained; however, an excess amount of the alkene and relatively high reaction temperatures and pressures were required. For terminal alkenes 136, the reaction was regioselective to give linear silanes; however, hydrosilylation products 137 were accompanied byproducts 138 arising from dehydrosilylation.…”

Hydrosilylation vs. dehydrogenative silylation of styrene catalysed by iron(0) carbonyl complexes with multivinylsilicon ligands – Mechanistic implications

“…It is well-recognized that iron complexes such as [Fe (CO) 5 ] at high temperature and/or upon UV irradiation under mild conditions catalyse both reactions, i.e. dehydrogenative silylation and hydrosilylation [8]. The mechanism proposed by Randolph and Wrighton assumed important role of irradiation in the formation of catalytically active [Fe(CO) 3 ] species via photodissociation of the FeeCO bond [9].…”