Synthesis and characterization of per/poly¯uorophenoxy derivatives of octachlorocyclotetraphosphazenes Krista L. Rule, Immanuel I. Selvaraj, Robert L. Kirchmeier * Department of Chemistry, University of Idaho, Moscow, ID 83844-2343, USA Received 31 July 2001; accepted 31 August 2001 Abstract Octachlorocyclotetraphosphazene was treated with various ¯uorinated phenols to form partially and completely substituted cyclotetra- phosphazenes. The mono-substitution reactions were carried out using a base in benzene while for complete substitution sodium salts of the corresponding phenoxides were used. All compounds were characterized by 1 H, 19 F, and 31 P NMR, IR and mass spectroscopic methods. A crystal structure was obtained for N 4 P 4 OC 6 F 5 ) 8 , and shows that the phosphazene ring is puckered. The angle of the planes N2P2N1P1N4 to N4P4N3P3N2 is 45.58 and the angle of the planes N1P1N4P4N3 to N3P3N2P2N1 is 43.88. # 2001 Elsevier Science B.V. All rights reserved. Keywords: Phosphazene; Tetramer; Fluoroalkoxide; Single crystal analysis 1. Introduction Cyclotriphosphazenes I), Fig. 1) are one of the most well studied inorganic heterocyclic systems known [1]. The linear analogue polyphosphazenes II) are well known for their use as membranes, polymer solid electrolytes, drug carriers, and ¯ame retardants, etc. [2]. Although studies of the cyclic trimer and the linear polyphosphazenes have been well documented, the cyclotetraphosphazene III) systems have not been well studied. Cyclotriphosphazenes contain- ing ¯uorinated phenoxy groups are useful as lubricants and for surface coatings in magnetic tapes and other end use applications [3,4]. The ultimate focus of our research is the preparation of organic polymers containing cyclotetrapho- sphazenes as pendant groups [5] and the characterization of these materials as surface coatings. In this study we report the synthesis and characterization of mono-, di-, and octa- substituted ¯uorophenoxycyclotetraphosphazenes. Some of these compounds have been reported previously but were poorly characterized [6]. 2. Experimental 2.1. Materials Octachlorocyclotetraphosphazene Otsuka Chemical Co., Ltd., Japan) was sublimed and recrystallized prior to use. Sodium hydride, triethylamine, p-¯uorophenol, penta¯uor- ophenol, p-tri¯uoromethyl-phenol Aldrich) were used as received. 4-Hydroxy-4 0 -vinylbiphenyl was synthesized according to [13]. 2.2. Methods 1 H and 19 F NMR spectra were obtained on a Bruker AC200 or Bruker AC300 instrument in CDCl 3 solvent. Chemical shift values were reported relative to TMS and CCl 3 F for proton and ¯uorine, respectively. Infrared spectra were recorded on a Perkin-Elmer 1710 FTIR spectrometer with KBr disks. Mass spectral data EI, FAB  , and accurate mass) were obtained using a Jeol JMS AX505HA mass spectrometer. 2.2.1. X-ray diffraction studies The X-ray diffraction data for compound 5 was collected on a Siemens SMART diffractometer with a CCD detector at 90 8C. Data collection parameters are listed in Table 1. The frame data were acquired with the SMART [14±17] software using a Siemens three-circle platform using Mo Ka radiation l  0:71073 A Ê ) from a ®ne-focus tube. The w- axis on this platform is ®xed at 54.748, and the diffract- ometer is equipped with a CCD detector maintained near 54 8C. Cell constants are determined from 60, 10 s, frames. A complete hemisphere of data is scanned on o 0.38) with a run time of 10s per frame at a detector resolution of 512  512 pixels. A total of 1271 frames were collected in three sets, and a ®nal set of 50 frames, were also Journal of Fluorine Chemistry 112 2001) 307±312 * Corresponding author. Fax: 1-208-885-6173. E-mail address: rlkirch@uidaho.edu R.L. Kirchmeier). 0022-1139/01/$ ± see front matter # 2001 Elsevier Science B.V. All rights reserved. PII:S0022-113901)00516-4