Phosphorus-nitrogen compounds. Part 20: Fully substituted spiro-cyclotriphosphazenic lariat (PNP-pivot) ether derivatives

OKUMUŞ A., Bilge S., Kilic Z., Ozturk A., HÖKELEK T., YILMAZ F.

Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, vol.76, no.3-4, pp.401-409, 2010 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 76 Issue: 3-4
  • Publication Date: 2010
  • Doi Number: 10.1016/j.saa.2010.04.007
  • Journal Name: Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.401-409
  • Keywords: spiro-Phosphazene, Lariat (PNP) ether, Spectroscopy, Crystal structure, Hydrogen bond, CRYPTA PHOSPHAZENE DERIVATIVES, MULTISITE COORDINATION LIGANDS, CYCLOPHOSPHAZENES, HEXACHLOROCYCLOTRIPHOSPHAZATRIENE, POLYPHOSPHAZENES, PRODUCTS, DIOXY, ANSA
  • Ankara University Affiliated: Yes

Abstract

The condensation reactions of partly substituted spiro-cyclotriphosphazenic lariat (PNP-pivot) ethers, N3P3[(o-NHPhO)2R]Cl4 [where R = -CH2CH2- (1) and -CH2CH2OCH2CH2- (2)] with morpholine and 1,4-dioxa-8-azaspiro[4,5]decane (DASD) produce fully substituted morpholino (3 and 4) and 1,4-dioxa-8-azaspiro[4,5]deca (5 and 6) phosphazenes. These are the new examples of the spiro-cyclophosphazenic lariat ether derivatives with N2Ox (x = 2 and 3) donor type containing 11- and 14-membered macrocycles. The solid state structures of 3, 5 and 6 have been determined by X-ray diffraction techniques. Compound 3 has intermolecular N-H...O hydrogen bond, compound 5 has intra- and intermolecular N-H...O hydrogen bonds, while compound 6 has intramolecular N-H...O and O-H...N and intermolecular N-H...O and O-H...O hydrogen bonds. The correlations of the endocyclic (α) and exocyclic (α′) NPN bond angles with δPspiro values are investigated. The structural investigations of 3-6 have been verified by elemental analyses, MS, FTIR, 1H, 13C and 31P NMR, DEPT and HETCOR techniques. © 2010 Elsevier B.V. All rights reserved.