The Noble Addendum of a Phosphenium Ligand to a Base Metal: Coordination, Activation, and Hydrogenation of Alkenes and Alkynes on a Chromium Complex.

The synthesis of a new bis-NHP complex (NHP=N-heterocyclic phosphenium) of chromium via salt metathesis and studies of its reactivity are reported. Photochemical reactions with H 2 and selected olefins give rise to non-isolable H 2 - and π-alkene complexes identified spectroscopically, while internal alkynes react via activation of the triple bond to yield isolable metalla-phospha-cyclobutenes characterized by spectroscopic and XRD data. DFT studies give a preliminary account of the bonding in H 2 - and alkene-complexes and explain the different reactivity towards alkenes and alkynes as the consequence of kinetic effects. Photolysis of the bis-NHP-complex in the presence of H 2 and olefins or alkenes enables the catalytic hydrogenation of the organic substrates, while the π-ethene complex mediates the catalytic hydrogenation of ethene in a dark reaction. The similarities and differences between both catalytic processes are shortly discussed.