A Rh(I) complex with an annulated N-heterocyclic carbene ligand for E-selective alkyne hydrosilylation

β-(Z)-Selective alkyne hydrosilylation by a N,O-functionalized NHC-based rhodium(i) catalyst

“…It is worth noting that the β-( Z ) selectivity observed in the hydrosilylation of 1-hexyne with HSiMe 2 Ph with rhodium( i ) catalysts 2–6 contrasts with that observed by Salazar and Bera with related cationic diene compounds based on NHC–Py 19 or NHC–naphthyridine 20 bidentate ligands with very bulky substituents on the NHC fragment, as both showed excellent β-( E ) selectivities in the hydrosilylation of a number of terminal alkynes.…”

“…This compound has been shown to be an excellent catalyst precursor for accessing β-( E )-vinylsilanes in the hydrosilylation of a range of terminal alkynes with the hydrosilanes Et 3 SiH and (EtO) 3 SiH. 20…”

“…This compound has been shown to be an excellent catalyst precursor for accessing β-(E)-vinylsilanes in the hydrosilylation of a range of terminal alkynes with the hydrosilanes Et 3 SiH and (EtO) 3 SiH. 20 Inspired by these results, we envisaged the potential of Rh (I) complexes based on a lutidine-derived polydentate ligand having NHC and methoxy side-donor functions as hydrosilylation catalysts. The incorporation of a flexible methoxy-methyl functionality, -CH 2 OMe, at the 6-position of the pyridine donor moiety, in close proximity to the rhodium centre, might have an impact on the outcome of the hydrosilylation reactions.…”

Rh(I) Complexes in Catalysis: A Five-Year Trend

“…Additionally, this Rh(I) complex showed high performances in the E/Z selective alkyne hydrosylilation. The catalyst produced the E-vinylsylane in excellent yields and high selectivity [56] (Scheme 6, Figure 2). Hydrosilylation and tandem isomerization-hydrosilylation of alkenes, on the other hand, were successfully performed by a family of rhodium complexes bearing an NHC ligand with an oxygen-containing pendant arm and differing for the derivatization on the O-donor [57] (Figure 2).…”

Synthesis and structure of thienyl Fischer carbene complexes of PtII for application in alkyne hydrosilylation

“…9 Considering the evidence for vinylsilane product formation via the standard Chalk-Harrod mechanism, the same mechanism is proposed for 2 and 1 (Scheme S2, ESI †). 9,34 Oxidative addition of the silane to the Pt metal centre is followed by chloride ligand dissociation. Alkyne migratory 1,2-insertion occurs into the Pt-H bond, followed by reductive elimination to give the b-E-isomer.…”