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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., N,N′ ‐Ethylene bridged bis‐2‐aryl pyrrolinium cations are reported in this work, which (a) undergo stepwise reversible two‐electron reduction coupled two hydrogen transfer to form E‐diaminoalkenes; and (b) have non identical pathways for reduction and oxidation.

PubMed ID: 30256354, Herein we report two different reactivity modes of lithium(aryl)(boryl)amide, 4, when it is reacted with chlorosilanes such as SiCl4 and MeSiHCl2, and chlorophosphine, Ph2PCl. Thus, the reaction of lithium(aryl)(boryl)amide, 4, with MeSiHCl2 leads exclusively to an N-substitution product, 6. On the other hand, the reaction of 4 with SiCl4 and Ph2PCl proceeds completely differently affording exclusively p-aryl-C-substitution products, 5 and 7, respectively. © 2018 The Royal Society of Chemistry., Department of Science and Technology, Ministry of Science and Technology Tata Institute of Fundamental Research, This work was supported by the TIFR Centre for Interdisciplinary Science Hyderabad, India and SERB-DST (EMR/2014/001237), India. V. C. is thankful to the Department of Science and Technology, New Delhi, India, for a National J. C. Bose fellowship. We are thankful to Professor Dr David Scheschkewitz, Saarland University, Saarbrücken, Germany, for facilitating the measurement of elemental analysis for compounds 4 and 7 and for the 7Li{1H} NMR of compound 4. We are also thankful to Professor Dr Biprajit Sarkar, Freie Universität Berlin, Berlin Germany for the elemental analysis for compounds 3, 5, and 6.