Phosphorus-nitrogen compounds: Part 45. Vanillinato-substituted cis- and trans-bisferrocenyldispirocyclotriphosphazenes: Syntheses, spectroscopic and crystallographic characterizations

• Published in: Journal of molecular structure Vol. 1181; pp. 235 - 243
• Main Authors: Tümer, Yasemin, Asmafiliz, Nuran, Arslan, Gönül, Kılıç, Zeynel, Hökelek, Tuncer
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 05-04-2019
• Subjects: Chiral solvating agent; Crystal structure; Ferrocenyldispirophosphazenes; Spectroscopy; Vanillin; Spectroscopy; Ferrocenyldispirophosphazenes; Vanillin; Chiral solvating agent; Crystal structure
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/j.molstruc.2018.12.090

The nucleophilic replacement reactions of one equimolar amount of the cis- and trans-bisferrocenyldispirocyclotriphosphazenes (1 and 2) with the one equimolar amount of the potassium salt of 4-hydroxy-3-methoxybenzaldehyde (potassium vanillinate) produce mono-vanillinato phosphazenes (3 and 4). When these reactions were carried out with the one equimolar amount of 1 and 2, and two equimolar amounts of potassium vanillinate gave bis-vanillinato ferrocenylphosphazenes (5 and 6). The structures of the new phosphazenes were characterized by FTIR, MS, 1H, 13C and 31P NMR spectral data. The solid-state structures of 3, 4, 5 and 6 were clarified by single crystal X-ray diffraction techniques. All the phosphazenes have stereogenic phosphorus atoms. Compound 3 has a pseudo asymmetric center. The absolute configurations of all the compounds were examined using X-ray crystallography. The chiral properties of 3 and 4 were also investigated by 31P NMR spectroscopy upon the addition of the chiral solvating agent (S)-(+)-2,2,2-trifluoro-1-(9′-anthryl)ethanol, CSA.
The syntheses, spectroscopic and crystallographic characterizations of the mono-and bis-vanillinato-substituted cis- and trans-dispirocycloferrocenylphosphazenes were carried out. The crystal structures and absolute configurations of all the new compounds were determined by X-ray crystallography. The chiral properties of mono-vanillinato-cis- and trans-phosphazenes were also assigned using 31P NMR spectroscopy upon the addition of CSA. [Display omitted]
•Vanillinato cis- and trans-dispiroferrocenylcyclotriphosphazenes were obtained.•Molecular and crystal structures of the new phosphazenes were determined.•The absolute configurations of the compounds are determined by crystallographic data.•Chirality of the compounds was interpreted using 31P NMR upon the addition of CSA.