title: Formation and electrochemical properties of a 1,4-diphosphafulvene including formal dimerization of phosphaallene.
abstract: Reactions of sterically protected 2-bromo-3-phenyl-1-phosphapropenes with bases such as tert-butyllithium and potassium tert-butoxide successfully afforded a bulky 1,4-diphosphafulvene (Mes = 2,4,6-tBu(3)C(6)H(2)) through a novel and formal dimerization pathway of 1-phosphaallene, together with small amounts of 3-phenyl-1-phosphaallene and 3,4-diphosphanylidenecyclobutene. The structure of the 1,4-diphosphafulvene was confirmed by X-ray crystallography indicating somewhat flattened phosphorus atoms due to the bulky Mes groups. The electrochemical properties of the 1,4-diphosphafulvene were investigated to show promising suitability as an electron donor, and indeed, it afforded a charge-transfer complex with TCNQ. Preparation and structural elucidation of an alkoxy-functionalized 1-phosphaallene was also performed, and the effect of the alkoxy group on the 1-phosphaallene moiety was characterized.
authors.affiliation: Department of Chemistry, Graduate School of Science, Tohoku University, Aoba, Sendai 980-8578, Japan.
authors.forename: Shigekazu
authors.initials: S
authors.lastname: Ito
authors.forename: Satoshi
authors.initials: S
authors.lastname: Sekiguchi
authors.forename: Masaaki
authors.initials: M
authors.lastname: Yoshifuji