Abstract
The preparation of α , ω-oligosiloxanediolsHOSiMe2O(SiPh2O)nSiMe2OH(5–8; n=1–4) by the mild oxidation of thecorresponding organo-H-siloxaneHSiMe2O(SiPh2O)nSiMe2H(1–4; n = 1–4) using Pearlman's catalyst,Pd(OH2)/C, is reported. Compounds 5–7 possessnew hydrogen bonding modes, whose influences on the Si–O chainconformation are discussed and compared with the published analoguesHOSiPh2OSiPh2OSiPh2OH (9),HOSit-Bu2OSiMe2OSit-Bu2OH (10) andHOSiPh2OSiPh2OSiPh2OSiPh2OH(11), whereas compound 8 appears to be polycrystalline.Preliminary results of the HCl-catalysed condensation of5–8 are also reported, which provided complex mixtures ofoligomeric products in the case of 5 and 8, and (almost)exclusivelycyclo-(Me2SiO)2(Ph2SiO)2(12) andcyclo-(Me2SiO)2(Ph2SiO)3(13) in the case of 6 and 7, respectively. Compounds5–7 and 13 were investigated by X-raycrystallography.
Similar content being viewed by others
References
Lickiss, P.D. 1995 Adv. Inorg. Chem. 42, 147-262.
Lickiss, P.D. 1996 The synthesis and structures of silanols. In Tailor-Made Silicon-Oxygen Compounds, pp. 47-59. Braunschweig: Vieweg.
Lickiss, P.D. 2001 Polysilanols. In Chemistry of Organic Silicon Compounds, Vol. 3, eds Z. Rappoport & Y. Apeloig, pp. 695-744. Chichester: John Wiley & Sons Ltd.
Noll, W. 1968 Chemistry and Technology of the Silicones. New York: Academic Press.
Semlyen, J.A. & Clarson, S.J. 1991 Siloxane Polymers. Engle-wood Cliffs, NJ: Prentice Hall.
Murugavel, R., Voigt, A., Walawalkar, M.G. & Roesky, H.W. 1996 Chem. Rev. 96 (6), 2205-2236.
King, L. & Sullivan, A.C. 1999 Coord. Chem. Rev. 189, 19-57.
Lorenz, V., Fischer, A., Giessmann, S., Gilje, J.W., Gun'ko, Y., Jacob, K. & Edelmann, F.T. 2000 Coord. Chem. Rev. 206–207, 321-368.
Beckmann, J. & Jurkschat, K. 2001 Coord. Chem. Rev. 215, 267-300.
Denmark, S.E. & Sweis, R.F. 2002 Chem. Pharma. Bull. 50 (12), 1531-1541.
Denmark, S.E. & Sweis, R.F. 2002 Acc. Chem. Res. 35 (10), 835-846.
Haiduc, I. & Edelmann, F.T. 1999 Supramolecular Organo-metallic Chemistry. Weinheim: VCH.
Matarasso-Tchiroukhine, E. 1990 J. Chem. Soc. Chem. Commun. (9), 681-682.
Schubert, U. & Lorenz, C. 1997 Inorg. Chem. 36 (6), 1258-1259.
Shi, M. & Nicholas, K.M. 1997 J. Chem. Res. Syn. (11), 400-401.
Tan, H., Yoshikawa, A., Gordon, M.S. & Espenson, J.H. 1999 Organometallics 18 (23), 4753-4757.
Adam, W., Mitchell, C.M., Saha-Möller, C.R. & Weichold, O. 1999 J. Am. Chem. Soc. 121 (10), 2097-2103.
Lee, M., Ko, S. & Chang, S. 2000 J. Am. Chem. Soc. 122 (48), 12011-12012.
Barnes, G.H., Jr. & Daughenbaugh, N.E. 1966 J. Org. Chem. 31 (3), 885-887.
Coupar, P.I., Jaffres, P.-A. & Morris, R.E. 1999 J. Chem. Soc. Dalton Trans. (13), 2183-2188.
Hirabayashi, K., Mori, A., Kawashima, J., Suguro, M., Nishihra, Y. & Hiyama, T. 2000 J. Org. Chem. 65 (17), 5342-5349.
Mori, K., Tano, M., Mizugaki, T., Ebitani, K. & Kaneda, K. 2002 New J. Chem. 26 (11), 1536-1538.
Pearlman, W.M. 1967 Tetrahedron Lett. (17), 1663-1664.
Tsuji, J. 1995 Palladium Reagents and Catalysts: Innovations in Organic Synthesis. Chichester: John Wiley & Sons.
Toebes, M.L., van Dillen, J.A. & de Jong, K.P. 2001 J. Mol. Catal. A173 (1–2), 75-98.
Mori, Y. & Seki, M. 2002 Heterocycles 58, 125-127.
Mori, Y. & Seki, M. 2003 J. Org. Chem. 68 (4), 1571-1574.
Card, R.J., Schmitt, J.L. & Simpson, J.M. 1983 J. Catal. 79 (1), 13-20.
Guisnet, M.R. 1990 Acc. Chem. Res. 23 (11), 392-398.
Beckmann, J., Dakternieks, D., Lim, A.E.K., Lim, K.F. & Jurkschat, K. 2004 Organometallics, submitted for publication.
Jeffrey, G.A. 1997 An Introduction to Hydrogen Bonding. New York: Oxford University Press.
Steiner, T. 2002 Angew. Chem. Int. Ed. Engl. 41 (1), 48-76.
Behbehani, H., Brisdon, B.J., Mahon, M.F., Molloy, K.C. & Mazhar, M. 1993 J. Organomet. Chem. 463 (1–2), 41-45.
Graalmann, O., Klingebiel, U., Clegg, W., Haase, M. & Sheldrick, G.M. 1984 Chem. Ber. 117 (9), 2988-2997.
Beckmann, J., Jurkschat, K., Müller, D., Rabe, S. & Schürman, M. 1999 Organometallics 18 (12), 2326-2330.
Andrianov, K.A., Slonimskii, G.L., Levin, V.Y., Godovskii, Y.K., Kuznetsova, I.K., Tsvankin, D.Y., Moskalenko, V.A. & Kuteinikova, L.I. 1970 Vysokomol. Soedin., Ser. A 12 (6), 1268-1276.
Fritzsche, A.K. & Price, F.P. 1970 Pol y. Prepr. 11 (2), 462-469.
Jancke, H., Engelhardt, G., Kriegsmann, H. & Keller, F. 1979 Plast. Massy 26 (11), 612-616.
Engelhardt, G. & Jancke, H. 1981 Polym. Bull. 5 (11–12), 577-584.
Babu, G.N., Christopher, S.S. & Newmark, R.A. 1987 Macro-molecules 20 (11), 2654-2659.
Kendrick, T.C., Parbhoo, B. & White, J.W. 1989 Siloxane polymers and copolymers. In Chemistry of Organic Silicon Compounds, Vol. 2, eds S. Patai & Z. Rappoport, pp. 1289-1361. Chichester: John Wiley & Sons Ltd.
Zavin, B.G., Strelkova, T.V., Kovalenko, S.I., Rabkina, A.Y., Sablina, G.F. & Ronova, I.A. 1993 Ph. Prikl. Spektrosk. 58 (5–6), 516-522.
Zavin, B.G., Rabkina, A.Y., Strelkova, T.V. & Ronova, J.A. 1996 Pol y. Prepr. 37 (2), 712-713.
Cypryk, M., Kazmierski, K., Fortuniak, W. & Chojnowski, J. 2000 Macromolecules 33 (5), 1536-1545.
Yang, M.H., Huang, W.J., Chien, T.C., Chen, C.M., Chang, H.Y., Chang, Y.S. & Chou, C. 2001 Polymer 42 (21), 8841-8846.
Brown, J.F. Jr. 1964 Fr. Patent 1356768.
Brown, J.F. Jr. & Prescott, P.I. 1964 J. Am. Chem. Soc. 86 (7), 1402-1409.
Sporck, C.R. & Coleman, A.E. 1965 J. Phys. Chem. 69 (3), 1066-1067.
Andrianov, K.A., Akushkina, S.E. & Guinava, L.N. 1966 Khim Geterotsikl. Soedin. (6), 944.
Shklover, V.E., Kalinin, A.E., Gusev, A.I., Bokii, N.G., Struchkov, Y.T., Andrianov, K.A. & Petrova, I.M. 1973 Zh. Strukt. Khim. 14 (4), 692-699.
SMART, SAINT and SADABS 1999 Siemens Analytical X-ray Instruments Inc. Madison, Wisconsin, USA.
Farrugia, L.J. 1997 J. Appl. Crystallogr. 20, 565.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Beckmann, J., Dakternieks, D., Duthie, A. et al. The use of Pearlman's catalyst for the oxidation of Si–H bonds. Synthesis, structures and acid-catalysed condensation of novel α, ω-oligosiloxanediols HOSiMe2O(SiPh2O)nSiMe2OH (n = 1−4). Silicon Chemistry 2, 27–36 (2003). https://doi.org/10.1023/B:SILC.0000047924.69957.b1
Issue Date:
DOI: https://doi.org/10.1023/B:SILC.0000047924.69957.b1