title: Unexpected Ring Expansion of a Four-Membered Cyclophosphazane.
abstract: Nucleophilic substitution reactions of the N(R),N(R)-spiro-bridged octachlorobis(cyclotriphosphazene), N3P3Cl4[N(CH2)5CH3]2N3P3Cl4 (1), with sodium salts of alcohols (1,3-propanediol, 2,2,3,3,4,4-hexafluoro-1,5-pentanediol, and phenol) give ansa products (2-4) via an unexpected rearrangement. These products were characterized by elemental analysis, mass spectrometry, and (1)H and (31)P NMR spectroscopy. The molecular structures of compounds 3 and 4 were also established by X-ray crystallography. This new class of phosphazene structures consists of three fused P3N3 rings that arise from expansion of the four-membered phosphazane ring in 1 to a six-membered N3P3 ring during alcoholysis reactions.
authors.affiliation: Department of Chemistry, Gebze Technical University , 41400 Gebze, Kocaeli, Turkey.
authors.forename: Serap
authors.initials: S
authors.lastname: Beşli
authors.affiliation: Department of Chemistry, Gebze Technical University , 41400 Gebze, Kocaeli, Turkey.
authors.forename: Ceylan
authors.initials: C
authors.lastname: Mutlu Balcı
authors.affiliation: Department of Chemistry, Gebze Technical University , 41400 Gebze, Kocaeli, Turkey.
authors.forename: Hakan
authors.initials: H
authors.lastname: Cantürk
authors.affiliation: Department of Chemistry, Gebze Technical University , 41400 Gebze, Kocaeli, Turkey.
authors.forename: Semih
authors.initials: S
authors.lastname: Doğan
authors.affiliation: Department of Chemistry, Gebze Technical University , 41400 Gebze, Kocaeli, Turkey.
authors.forename: Fatma
authors.initials: F
authors.lastname: Yuksel
authors.affiliation: Department of Chemistry, University of Vermont , Burlington, Vermont 05405-0125, United States.
authors.forename: Christopher W
authors.initials: CW
authors.lastname: Allen
mesh_terms: D018360:Crystallography, X-Ray; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009943:Organophosphorus Compounds / Q000737:chemistry*; D011409:Propylene Glycols / Q000737:chemistry
chemical_list: D009943:Organophosphorus Compounds; D011409:Propylene Glycols; C041787:1,3-propanediol