Multistimuli-Responsive [3]Dioxaphosphaferrocenophanes with Orthogonal Switches

Novel multistimuli-responsive phosphine ligands comprising a redox-active [3]dioxaphosphaferrocenophane backbone and a P-bound imidazolin-2-ylidenamino entity that allows switching by protonation are reported. Investigation of the corresponding metal complexes and their redox behaviour are reported and show the sensitivity of the system towards protonation and metal coordination. The experimental findings are supported by DFT calculations. Protonation and oxidation events are applied in Rh-catalysed hydrosilylations and demonstrate a remarkable influence on reactivity and/or selectivity.

Automated summary

Novel multistimuli-responsive phosphine ligands with a redox-active structure capable of switching by protonation have been reported. The experimental results demonstrate the sensitivity of the system to protonation and metal coordination, and show a significant influence on reactivity and/or selectivity in Rh-catalysed hydrosilylations.