Photo-triggered hydrogen atom transfer from an iridium hydride complex to unactivated olefins.

Chemical Science
Mirjam R SchreierOliver S Wenger

Abstract

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 exci...Continue Reading

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Citations

Jul 16, 2021·Journal of the American Chemical Society·Nidhi Kaul, Reiner Lomoth
Jun 23, 2021·Chemistry : a European Journal·Sier SangSven Schneider

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Methods Mentioned

BETA
irradiating
NMR

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