The synthesis and structure of triphenylsiloxycyclotriphosphazenes
Corresponding Author
Harry R. Allcock
Department of Chemistry, The Pennsylvania State University, University Park, PA 16802
Department of Chemistry, The Pennsylvania State University, University Park, PA 16802Search for more papers by this authorDavid J. Brennan
Department of Chemistry, The Pennsylvania State University, University Park, PA 16802
Search for more papers by this authorRobert R. Whittle
Department of Chemistry, The Pennsylvania State University, University Park, PA 16802
Search for more papers by this authorCorresponding Author
Harry R. Allcock
Department of Chemistry, The Pennsylvania State University, University Park, PA 16802
Department of Chemistry, The Pennsylvania State University, University Park, PA 16802Search for more papers by this authorDavid J. Brennan
Department of Chemistry, The Pennsylvania State University, University Park, PA 16802
Search for more papers by this authorRobert R. Whittle
Department of Chemistry, The Pennsylvania State University, University Park, PA 16802
Search for more papers by this authorAbstract
The triphenylsiloxy-substituted cyclotriphosphazenes, N3P3Cl5OSiPh3, gem-N3P3Cl4(OSiPh3)2, N3P3(OSiPh3)6, and N3P3(OPh)5OSiPh3, have been prepared. The synthesis of gem-N3P3Cl4(OSiPh3)2 involves the reaction of (NPCl2)3 with Ph3SiONa to form the intermediates gem-N3P3Cl4(OSiPh3)2(ONa) and gem-N3P3Cl4(ONa)2, which yield gem-N3P3Cl4(OSiPh3)2 when treated with Ph3SiCl. The compounds N3P3Cl5OSiPh3 and N3P3(OSiPh3)0 are formed by the condensation reactions of N3P3Cl5OBun and N3P3(OBun)6, respectively, with Ph3SiCl. The compound N3P3(OPh)5OSiPh3 is synthesized by the reaction between N3P3(OPh)5Cl and Et3SiONa to first give the intermediate N3P3(OPh)5ONa, which yields N3P3(OPh)5OSiPh3 when reacted with Ph3SiCl. The structural characterization and properties of these compounds are discussed. The crystal and molecular structure of gem-N3P3Cl4(OSiPh3)2 has been investigated by single-crystal X-ray diffraction techniques. The crystals are monoclinic with the space group P21/c with a = 16.850(8), b = 12.829(4), c = 18.505(15) Å, and β = 101.00(6)° with V = 3927 Å3 and Z = 4. © 1996 John Wiley & Sons, Inc.
References
- 1 H. R. Allcock, D. J. Brennan, R. J. Allen, Inorg. Chem., 18, 1985, 139.
- 2 H. R. Allcock, D. J. Brennan, J. M. Graaskamp, M. Parvez, Organometallics, 5, 1986, 2434.
- 3 H. R. Allcock, D. J. Brennan, J. M. Graaskamp, Macromolecules, 21, 1988, 1.
- 4 H. R. Allcock, D. J. Brennan, B. S. Dunn, M. Parvez, Inorg. Chem., 27, 1988, 3226.
- 5 H. R. Allcock, D. J. Brennan, J. Organomet. Chem., 341, 1988, 231.
- 6 H. R. Allcock, D. J. Brennan, B. S. Dunn, Macromolecules, 22, 1989, 1534.
- 7 H. R. Allcock, W. D. Coggio, R. S. Archibald, D. J. Brennan, Macromolecules, 22, 1989, 3571.
- 8 H. R. Allcock, W. D. Coggio, Macromolecules, 23, 1990, 1626.
- 9 D. J. Brennan, J. Graaskamp, B. S. Dunn, H. R. Allcock, Inorg. Synth., 25, 1989, 60.
- 10 W. D. Coggio, D. J. Brennan, R. S. Archibald, H. R. Allcock, Polym. Prepr. (ACS Polym. Div.), 30, 1989, 204.
- 11 H. R. Allcock, W. D. Coggio, M. Parvez, M. L. Turner, Organometallics, 10, 1991, 677.
- 12 H. R. Allcock, C. J. Nelson, W. D. Coggio, Organometallics, 19, 1991, 3819.
- 13 H. R. Allcock, W. D. Coggio, Macromolecules, 26, 1993, 764.
- 14 H. R. Allcock, C. J. Nelson, W. D. Coggio, I. Manners, W. J. Koros, D. R. B. Walker, L. A. Pessan, Macromolecules, 26, 1993, 1493.
- 15 H. R. Allcock, D. E. Smith, Y.-B. Kim, J. J. Fitzgerald, Macromolecules, 27, 1994, 5206.
- 16 S. E. Kuharcik, D. E. Smith, C. J. Nelson, H. R. Allcock, J. J. Fitzgerald, Polym. Mater. Sci. Eng. Prepr. (ACS Div. Polym. Mater.), 71, 1994, 542.
- 17 H. R. Allcock, D. E. Smith, Chem. Mater., 1995, in press.
- 18 H. R. Allcock, S. E. Kuharcik, J. Inorg. Organomet. Polym., 4(4), 1995, in press.
- 19 J. E. Mark, H. R. Allcock, R. West (eds.): Inorganic and Organometallic Polymers, Prentice Hall, Englewood Cliffs, NJ, Chap. 3 (1992).
- 20 H. R. Allcock, Acc. Chem. Res., 12, 1979, 351.
- 21
S. N. Borisov,
M. G. Voronkov,
E. Ya. Lukevits:
Organosilicon Derivatives of Phosphorus and Sulfur,
Plenum Press, New York-London,
chap. 1
(1971)
10.1007/978-1-4684-0727-3 Google Scholar
- 22 H. R. Allcock, S. E. Kuharcik, Inorg. Organomet. Polym., 5(1), 1996, in press.
- 23 H. R. Allcock, D. J. Brennan, R. W. Allen, Macromolecules, 18, 1985, 139.
- 24(a) S. M. Zhivukhin, V. B. Tolstoguzov, A. I. Ivanov, Russ. J. Inorg. Chem., 7, 1962, 1134. (b) S. I. Belykh, S. M. Zhivukhin, V. V. Kireev, G. S. Kolesnikov, Russ. J. Inorg. Chem., 14(5), 1969, 668.
- 25 H. R. Allcock: Phosphorus-Nitrogen Compounds. Cyclic, Linear, and High Polymeric Systems, Academic Press, New York (1972).
- 26 H. R. Allcock, R. L. Kugel, J. Am. Chem. Soc., 87, 1965, 4216.
- 27 H. R. Allcock, R. L. Kugel, K. J. Valan, Inorg. Chem., 5, 1966, 1709.
- 28
S. I. Belykh,
S. M. Zhivukhin,
V. V. Kireyev,
H. S. Kolesnikov,
Polym. Sci. USSR,
11,
1969,
711.
10.1016/0032-3950(69)90061-6 Google Scholar
- 29 B. W. Fitzsimmons, C. Hewlett, K. Hills, R. A. Shaw, J. Chem. Soc. (A), 1964, 1735.
- 30 A. A. Volodin, S. N. Zelenetskii, V. V. Kireev, V. V. Korshak, J. Gen. Chem. USSR, 45, 1975, 32.
- 31 K. S. Dhathathreyan, S. S. Krishnamurthy, A. R. Vasudeva Murthy, R. A. Shaw, M. Woods, J. Chem. Soc. Dalton Trans., 27, 1982, 1549.
- 32 H. R. Allcock, M. S. Connolly, R. R. Whittle, Organometallics, 2, 1983, 1514.
- 33 H. R. Allcock, P. R. Suszko, L. J. Wagner, R. R. Whittle, B. Boso, J. Am. Chem. Soc., 106, 1984, 4966.
- 34 G. J. Bullen, J. Chem. Soc. (A), 1971, 1450.
- 35 W. C. Marsh, J. Trotter, J. Chem. Soc. (A), 1971, 169.
- 36 G. B. Ansell, G. J. Bullen, J. Chem. Soc. (A), 1971, 2498.
- 37
N. G. Bokii,
G. N. Zakharova,
Yu. T. Struchkov,
J. Struct. Chem.,
13,
1972,
267.
10.1007/BF00744498 Google Scholar
- 38 M. A. Hossain, M. B. Hursthouse, K. M. A. Malik, Acta Crystallogr., B35, 1979, 522.
- 39 M. F. Sorokin, V. K. Latov, J. Gen. Chem. USSR, 35, 1965, 1472.
- 40 B. Dishon, J. Am. Chem. Soc., 81, 1949, 2251.
- 41 B. W. Fitzsimmons, R. A. Shaw, J. Chem. Soc., 1964, 1735.
- 42 E. T. McBee, K. Okuhara, C. J. Morton, Inorg. Chem., 5, 1966, 450.
- 43 H. R. Allcock, T. L. Evans, T. J. Fuller, Inorg. Chem., 19, 1980, 1026.
- 44 All programs used in data collection, reduction, and refinement were part of the Enraf-Nonius Structure Determination Package (SDP), Enraf-Nonius, Delft, Holland, 1975, revised 1977.
- 45 Main, P. MULTAN 78. A system of computer programs for the automatic solutions of crystal structures. Dept. of Physics, University of York, York, England, 1978; obtained from J. G. Williams, Brookhaven National Labs., Upton, NY.
- 46 Isotropic thermal parameters are of the form exp [ −B(sin2 θ/λ2]. Anisotropic thermal parameters are of the form exp [−2π2(U11a*2h2 + U22b*2k2 + U33c*2l2 + 2U12a*b*hk + 2U13a*c*hl + 2U23b*c*kl)].
- 47(a) D. T. Cromer, J. B. Mann, Acta Crystallogr., A24, 1968, 321; (b) R. F. Stewart, E. R. Davidson, W. T. Simpson, J. Chem. Phys. 42, 1965, 3175.
- 48 International Tables for X-ray Crystallography, vol. IV, Knyoch Press, Birmingham, England (1968).
