title: Phosphorus centers of different hybridization in phosphaalkene-substituted phospholes.
abstract: Phosphole-substituted phosphaalkenes (PPAs) of the general formula Mes*P=C(CH(3))-(C(4)H(2)P(Ph))-R 5 a-c (Mes*=2,4,6-tBu(3)Ph; R=2-pyridyl (a), 2-thienyl (b), phenyl (c)) have been prepared from octa-1,7-diyne-substituted phosphaalkenes by utilizing the Fagan-Nugent route. The presence of two differently hybridized phosphorus centers (σ(2) ,λ(3) and σ(3) ,λ(3)) in 5 offers the possibility to selectively tune the HOMO-LUMO gap of the compounds by utilizing the different reactivity of the two phosphorus heteroatoms. Oxidation of 5 a-c by sulfur proceeds exclusively at the σ(3) ,λ(3) -phosphorus atom, thus giving rise to the corresponding thioxophospholes 6 a-c. Similarly, 5 a is selectively coordinated by AuCl at the σ(3),λ(3) -phosphorus atom. Subsequent second AuCl coordination at the σ(2),λ(3) -phosphorus heteroatom results in a dimetallic species that is characterized by a gold-gold interaction that provokes a change in π conjugation. Spectroscopic, electrochemical, and theoretical investigations show that the phosphaalkene and the phosphole both have a sizable impact on the electronic properties of the compounds. The presence of the phosphaalkene unit induces a decrease of the HOMO-LUMO gap relative to reference phosphole-containing π systems that lack a P=C substituent.
authors.affiliation: Department of Chemistry, Ångström Laboratories, Uppsala University, Box 523, 75120 Uppsala (Sweden), Fax: (+46) 18-471-6844.
authors.forename: Elisabet
authors.initials: E
authors.lastname: Öberg
authors.forename: Andreas
authors.initials: A
authors.lastname: Orthaber
authors.forename: Christophe
authors.initials: C
authors.lastname: Lescop
authors.forename: Régis
authors.initials: R
authors.lastname: Réau
authors.forename: Muriel
authors.initials: M
authors.lastname: Hissler
authors.forename: Sascha
authors.initials: S
authors.lastname: Ott
keywords: X-ray diffraction; conjugation; electronic structure; phosphaalkenes; phosphorus