C,C-Diacetylenic Phosphaalkenes as Heavy Diethynylethene Analogues
2009 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 74, no 24, 9265-9273 p.Article in journal (Refereed) Published
A series of C,C-diacetylenic phosphaalkenes 1b-e has been prepared from 1-chloropenta-1,2-dien-4-ynes 6b-e in a reaction with Mes*PCl2 (Mes* = 2,4,6-(Bu-1)(3)Ph) in the presence of LDA. Under identical conditions, isomeric butadiyne-substituted phosphaalkenes 2e-f can be obtained from 3-chloropenta-1,4-diyiies 5c-f. The title compounds represent rare examples of diethynylethenes in which a constituting methylene has been replaced by a phosphorus center. The formation of both isomers can be rationalized by a common pathway that involves isomeric allenyllithium species. Spectroscopic, electrochemical, and theoretical investigations show that the phosphorus heteroatoms are an intrinsic part of the compounds' pi-systems and lead to decreased HOMO-LUMO gaps compared to those in all-carbon-based reference compounds.
Place, publisher, year, edition, pages
2009. Vol. 74, no 24, 9265-9273 p.
IdentifiersURN: urn:nbn:se:uu:diva-127389DOI: 10.1021/jo901942uISI: 000272462100002OAI: oai:DiVA.org:uu-127389DiVA: diva2:329788