Cyclic Group 15 Radical Cations1. Issue 25 (8th May 2015)

• Record Type: Journal Article
• Authors: Brückner, Angelika; Hinz, Alexander; Priebe, Jacqueline B.; Schulz, Axel; Villinger, Alexander
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 25(2015)
• Page Start: 7426
• Page End: 7430
• Publication Date: 2015-05-08
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201502054
• Languages: English
• ISSNs: 1433-7851

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Singlet cyclo‐1, 3‐dipnicta‐2, 4‐diazane‐1, 3‐diyls of the type [E(μ‐NTer)₂E] (<bold>2</bold>, E=P, As, Ter=2, 6‐dimesitylphenyl) can undergo a one‐electron‐oxidation utilizing silver salts of weakly coordinating anions such as [AgL_{<italic>n</italic>}][B(C₆F₅)₄] (L=donor solvents) to afford the novel cyclic radical cations, [E(μ‐NTer)₂E]^+. (<bold>3</bold>^+.). When smaller and more basic anions were employed in the reaction, the anions were found to form covalent bonds to the radical centers yielding dipnictadiazanes, [FP(μ‐NTer)₂PF] (<bold>5</bold>) and [(CF₃CO₂)P(μ‐NTer)₂P(CF₃CO₂)] (<bold>6</bold>). A two‐electron oxidation process, resulting in the formation of dications of the type [E(μ‐NTer)₂E]²⁺, could not be observed. Computational and EPR data revealed that the spin density is almost completely localized at the two heavier pnictogen centers E of the former 1, 3‐dipnictadiazane‐1, 3‐diyls. The bonding situation in the radical cations features a rare example of a transannular one‐electron π bond without having a σ bond.</p> </abstract>