Group 9 open-shell organometallics: reactivity at the ligand

The main finding of this thesis is that the concept of ligand redox non-innocence can be utilized not only in stoichiometric, but also in catalytic reactions. We showed that one-electron activation of the coordinated ligand results in a dramatic change in the reactivity pathways, which may also allow for reactions with otherwise unreactive substrates. We also claim that a better understanding of the behavior of unsaturated ligands bound to paramagnetic (Group 9) metals can lead to useful, new (catalytic) transformations. Thus, we speculate on the possible involvement of carbene radical complexes in new (catalytic) reactions, which might potentially lead to valuable new products via unprecedented catalytic pathways. We propose that reactions of radical carbenes with conjugated dienes or reactions of radical vinylcarbenes with olefins could lead to functionalized cyclopentenes. We also postulate that nitrene ligands should be redox active and thus react via radical type mechanisms.