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This account reports on the fundamental principles of photoinduced bond activation through reductive elimination and oxidative addition reactions at group 8 and group 9 metal dihydrides. A recap of the seminal studies on the two elementary steps is presented. In addition, new developments employing laser pump-NMR probe methods are described with relevant examples. Kinetic and thermodynamic selectivities on C–H, C–C, C–F, B–H and Si–H bond activations are discussed.

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