title: Activation of small molecules by phosphorus biradicaloids.
abstract: The reactivity of biradicaloid [P(μ-NTer)]2 was employed to activate small molecules bearing single, double, and triple bonds. Addition of chalcogens (O2 , S8 , Sex and Tex ) led to the formation of dichalcogen-bridged P2 N2 heterocycles, except from the reaction with molecular oxygen, which gave a P2 N2 ring featuring a dicoordinated P(III) and a four-coordinated P(V) center. In formal [2πe+2πe] addition reactions, small unsaturated compounds such as ethylene, acetylene, acetone, acetonitrile, tolane, diphenylcarbodiimide, and bis(trimethylsilyl)sulfurdiimide are readily added to the P2 N2 heterocycle of the biradicaloid [P(μ-NTer)]2 , yielding novel heteroatom cage compounds. The synthesis, reactivity, and bonding of the biradicaloid [P(μ-NTer)]2 were studied in detail as well as the synthesis, properties, and structural features of all addition products.
authors.affiliation: Institut für Chemie, Universität Rostock, Albert-Einstein-Strasse 3a, 18059 Rostock (Germany) www.schulz.chemie.uni-rostock.de/
authors.forename: Alexander
authors.initials: A
authors.lastname: Hinz
authors.forename: Rene
authors.initials: R
authors.lastname: Kuzora
authors.forename: Uwe
authors.initials: U
authors.lastname: Rosenthal
authors.forename: Axel
authors.initials: A
authors.lastname: Schulz
authors.forename: Alexander
authors.initials: A
authors.lastname: Villinger
keywords: addition reactions; cage compounds; radical reactions; structure elucidation; synthetic methods