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N , N′ ‐Ethylene‐Bridged Bis‐2‐Aryl‐Pyrrolinium Cations to E ‐Diaminoalkenes: Non‐Identical Stepwise Reversible Double‐Redox Coupled Bond Activation Reactions
Author(s) -
Nayak Mithilesh Kumar,
Stubbe Jessica,
Neuman Nicolás I.,
Narayanan Ramakirushnan Suriya,
Maji Sandipan,
Schulzke Carola,
Chandrasekhar Vadapalli,
Sarkar Biprajit,
Jana Anukul
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202000255
Subject(s) - dication , redox , chemistry , electron transfer , electrochemistry , molecule , aryl , radical ion , reversible reaction , photochemistry , combinatorial chemistry , computational chemistry , ion , inorganic chemistry , organic chemistry , catalysis , alkyl , electrode
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.