15895-87-1Relevant articles and documents
A polymer-supported iridium catalyst for the stereoselective isomerisation of double bonds
Baxendale, Ian R.,Lee, Ai-Lan,Ley, Steven V.
, p. 516 - 518 (2002)
A polymer-supported iridium catalyst has been prepared and used in the isomerisation of the double bonds in aryl allylic derivatives with excellent trans selectivity and without the need for conventional work-up procedures.
Photo-triggered hydrogen atom transfer from an iridium hydride complex to unactivated olefins
Guo, Xingwei,Pfund, Bj?rn,Schreier, Mirjam R.,Wenger, Oliver S.
, p. 8582 - 8594 (2020/09/07)
Many photoactive metal complexes can act as electron donors or acceptors upon photoexcitation, but hydrogen atom transfer (HAT) reactivity is rare. We discovered that a typical representative of a widely used class of iridium hydride complexes acts as an H-atom donor to unactivated olefins upon irradiation at 470 nm in the presence of tertiary alkyl amines as sacrificial electron and proton sources. The catalytic hydrogenation of simple olefins served as a test ground to establish this new photo-reactivity of iridium hydrides. Substrates that are very difficult to activate by photoinduced electron transfer were readily hydrogenated, and structure-reactivity relationships established with 12 different olefins are in line with typical HAT reactivity, reflecting the relative stabilities of radical intermediates formed by HAT. Radical clock, H/D isotope labeling, and transient absorption experiments provide further mechanistic insight and corroborate the interpretation of the overall reactivity in terms of photo-triggered hydrogen atom transfer (photo-HAT). The catalytically active species is identified as an Ir(ii) hydride with an IrII-H bond dissociation free energy around 44 kcal mol-1, which is formed after reductive 3MLCT excited-state quenching of the corresponding Ir(iii) hydride, i.e. the actual HAT step occurs on the ground-state potential energy surface. The photo-HAT reactivity presented here represents a conceptually novel approach to photocatalysis with metal complexes, which is fundamentally different from the many prior studies relying on photoinduced electron transfer. This journal is
A selective and convenient ruthenium mediated method for the synthesis of mixed acetals and orthoesters
Krompiec, Stanis?aw,Penczek, Robert,Ku?nik, Nikodem,Ma?ecki, Jan Grzegorz,Matlengiewicz, Marek
, p. 137 - 140 (2007/10/03)
Addition of alcohols and phenols to O-allyl compounds (allyl ethers and acrolein acetals), catalyzed by [RuCl2(PPh3)3], was examined. Intramolecular addition of an OH group, leading to the formation of cyclic acetals and o
