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- Arkhypchuk, Anna I., et al.
(author)
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Versatile Approach to 3-Phosphahexatrienes Bearing Low Coordinated Phosphorus
- 2015
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In: Phosphorus Sulfur and Silicon and the Related Elements. - : Informa UK Limited. - 1042-6507 .- 1563-5325. ; 190:5-6, s. 638-646
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Journal article (peer-reviewed)abstract
- lambda(3)-phosphahexatrienes were prepared from ethoxyvinyl phosphinophosphonates using the phospha-Wittig-Horner reaction. The title compounds can be easily prepared in three steps starting from dichlorophosphines with good overall yields. Although these were found to be thermally unstable, these can be trapped, for instance, with methanol. The resulting methoxyphosphines are isolated in high yields in case of aldehyde starting materials with more bulky substituents.
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3. |
- Svyaschenko, Yurii V., et al.
(author)
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Tuning the Electronic Properties of Acetylenic Fluorenes by Phosphaalkene Incorporation
- 2016
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In: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 22:12, s. 4247-4255
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Journal article (peer-reviewed)abstract
- Versatile synthetic protocols for 2,7- and 3,6-diacetylenic fluorene-9-ylidene phosphanes (F9Ps) were developed. Protodesilylation of trimethylsilyl-protected acetylenic F9Ps affords terminal acetylenes that can be employed in Sonogashira and Glaser-type C-C coupling reactions to give thienyl-decorated and butadiyne-bridged fluorene-9-ylidene phosphanes, respectively. As evidenced by UV/Vis spectroscopy and cyclic voltammetry and corroborated by ab initio calculations, the presence of the P center in the F9Ps induces a significantly reduced HOMO-LUMO splitting that originates from stabilization of the LUMO levels. Variation of the acetylene substitution pattern is an additional tool to influence the optical and electronic properties. Whereas 3,6-disubstituted F9Ps have strong absorptions around 400nm, mainly due to -* transitions, 2,7-diacetylenic F9Ps exhibit longest-wavelength absorptions that have significant charge-transfer character with an onset around 520nm.
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