Abstract
This work presents a stepwise reversible two‐electron transfer induced hydrogen shift leading to the conversion of a bis‐pyrrolinium cation to an E‐diaminoalkene and vice versa. Remarkably, the forward and the reverse reaction, which are both reversible, follow two completely different reaction pathways. Establishing such unprecedented property in this type of processes was possible by developing a novel synthetic route towards the starting dication. All intermediates involved in both the forward and the backward reactions were comprehensively characterized by a combination of spectroscopic, crystallographic, electrochemical, spectroelectrochemical, and theoretical methods. The presented synthetic route opens up new possibilities for the generation of multi‐pyrrolinium cation scaffold‐based organic redox systems, which constitute decidedly sought‐after molecules in contemporary chemistry.
Highlights
This work presents a stepwise reversible two-electron transfer induced hydrogen shift leading to the conversion of a bis-pyrrolinium cation to an E-diaminoalkene and vice versa
This is because the frontier orbitals of transition metal complexes are readily tunable and accessible for reversible electron transfer
There are some recent examples in contemporary chemistry based on pblock elements which provide an alternative to the traditional paradigm of transition metal chemistry.[4]
Summary
This work presents a stepwise reversible two-electron transfer induced hydrogen shift leading to the conversion of a bis-pyrrolinium cation to an E-diaminoalkene and vice versa. Upon one-electron reductions to compounds 4H and 4Me new bands appear in the visible region at 346 and 478 nm and at 347 and 492 nm, respectively (Figures S12 and S13 in Supporting Information).
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