Affiliation:
1. Department of Chemistry and Applied Biosciences ETH Zürich Vladimir-Prelog-Weg 1–5/10 8093 Zürich Switzerland
2. Lehn Institute of Functional Materials (LIFM) School of Chemistry Sun Yat-Sen University 510275 Guangzhou China
3. State Key Laboratory of Elemento-Organic Chemistry Nankai University 30071 Tianjin China
Abstract
AbstractReaction of the imidazolium‐stabilized diphosphete‐diide IDP with trityl phosphaalkyne affords a mixture which contains the molecules 1 a and 1 b with a central C3P3 core, which formally carries a two‐fold negative charge. In order to avoid the formation of an antiaromatic 8π electron system within a conjugated dianionic six‐membered [C3P3]2− ring, 1 a adopts a bicyclic [3.1.0] and 1 b a tricyclic [2.2.0.0] structure which are in a dynamic equilibrium. 1 a, b can be reversibly oxidized to a triphosphinine dication [5]2+ with a central flat aromatic six‐membered C3P3 ring. This two‐electron redox reaction occurs in two single‐electron transfer steps via the 7π‐radical cation [4]⋅+, which could also be isolated and fully characterized. The profound reversible structural change observed for the two‐electron redox couple [5]2+/1 a, b is in sharp contrast to the C6H6/[C6H6]2− couple, which undergoes only a modest structural deformation.
Funder
Deutsche Forschungsgemeinschaft
Eidgenössische Technische Hochschule Zürich
Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung
National Natural Science Foundation of China
Subject
General Chemistry,Catalysis