title: Tunable Cyclopentane-1,3-diyls Generated by Insertion of Isonitriles into Diphosphadiazanediyls.
abstract: Diphosphadiazanediyl ([P(μ-NTer)]2, 1) is known to readily react with small molecules bearing multiple bonds to give [2.1.1]bicyclic species. On the contrary, in the reaction of isonitriles with 1, planar five-membered heterocycles (3) with biradical character are formed by insertion of the carbon atom into one P-N bond. Under irradiation, heterocyclic biradicaloids 3 are shown to generate housane-type [2.1.0]bicyclopentanes by transannular bond formation. However, these housane species thermally equilibrate, reforming the open-shell singlet cyclopentanediyl. The biradical character of 3 indicates high reactivity which is further demonstrated in the activation of small molecules bearing multiple bonds leading to [2.2.1]bicyclic heterocycles. Depending on the substituent of the isonitrile, the reaction with a second equivalent of isonitrile is also observed for smaller substituents. By employing suitable diisonitriles, even the catenation of two open-shell singlet cyclopentane-1,3-diyls is achieved. CASSCF(6,6) computations revealed biradical character for 3 ranging between 26 and 27%.
authors.affiliation: †Institut für Chemie, Abteilung Anorganische Chemie, Universität Rostock, Albert-Einstein-Straße 3a, 18059 Rostock, Germany.
authors.forename: Alexander
authors.initials: A
authors.lastname: Hinz
authors.affiliation: †Institut für Chemie, Abteilung Anorganische Chemie, Universität Rostock, Albert-Einstein-Straße 3a, 18059 Rostock, Germany.|‡Abteilung Materialdesign, Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Straße 29a, 18059 Rostock, Germany.
authors.forename: Axel
authors.initials: A
authors.lastname: Schulz
authors.affiliation: †Institut für Chemie, Abteilung Anorganische Chemie, Universität Rostock, Albert-Einstein-Straße 3a, 18059 Rostock, Germany.
authors.forename: Alexander
authors.initials: A
authors.lastname: Villinger