Phosphorus–nitrogen compounds: Part V. Phenolysis of p-trichloro-n-dichlorophosphorylmonophosphazene and the crystal structure of 1-(dichlorophosphinyl)-2-chloro-2,2-bis(2,4,6-tri-tert-butylphenoxy)phosphazene

• Published in: Journal of molecular structure 2000-01, Vol.516 (2-3), p.255-262
• Main Authors: Kılıç, A, Begeç, S, Kılıç, Z, Hökelek, T
• Format: Article
• Language: English
• Subjects: Crystal structures of phosphazene compounds; Phenolysis of acyclic monophosphazene; Phosphorus–nitrogen compounds; Spectroscopic studies of phosphazene derivatives
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/S0022-2860(99)00232-X

The reactions of Cl3PN–P(0)Cl2 (1) with Sodium 2,4,6-tert-butylphenoxide and sodium 2,6-di-tert-butyl-4-methylphenoxide give geminal bis products (2) and (3), respectively. Compounds (2) and (3) have been characterised by elemental analysis, IR, 1H-, 13C- and 31P-NMR and the structure of compound (2) has been examined crystallographically. It crystallizes in the monoclinic space group P21/n with a=10.056(1), b=25.986(1), c=15.533(1)Å, β=95.9(1)°, V=4037.6(1)Å3, Z=4 and Dx=1.19gcm−3. The bulky substituents are instrumental in determining the molecular geometry. The P–N bonds have neither single-nor double-bond character and are substantially shorter than the ideal P–N single bond. The PO double bond is abnormally long and it has a single bond character. The P–N–P angle [158.0(3)°] is the largest one for the reported acyclic phosphazene derivatives in the literature.