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- Title
Phosphorus Centers of Different Hybridization in Phosphaalkene-Substituted Phospholes.
- Authors
Öberg, Elisabet; Orthaber, Andreas; Lescop, Christophe; Réau, Régis; Hissler, Muriel; Ott, Sascha
- Abstract
Phosphole-substituted phosphaalkenes (PPAs) of the general formula Mes*PC(CH3)(C4H2P(Ph))R 5 a- c (Mes*=2,4,6- tBu3Ph; 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 (σ2,λ3 and σ3,λ3) 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 σ3,λ3-phosphorus atom, thus giving rise to the corresponding thioxophospholes 6 a- c. Similarly, 5 a is selectively coordinated by AuCl at the σ3,λ3-phosphorus atom. Subsequent second AuCl coordination at the σ2,λ3-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 PC substituent.
- Subjects
PHOSPHOLES; HETEROCYCLIC compounds; OXIDATION; NONMETALS
- Publication
Chemistry - A European Journal, 2014, Vol 20, Issue 27, p8421
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201402406