Summary.
Metal-alkoxides containing polymerizable groups are regularly used as precursors for inorganic–organic hybrid materials applying the combination of the sol–gel process and organic polymerizations. Here we report the synthesis of acetoacetoxy derivatives that are linked to methacrylate groups via alkyl chains of different chain length. The coordination of the resulting molecules to titanium- and zirconium-alkoxides (M(OR)4; M = Ti, Zr; R = ethyl, butyl, isopropyl) was investigated applying NMR and FT-IR measurements. The results were related to structural data of the dinuclear complex [Ti(Oi Pr)3(EAA)]2 (HEAA: ethyl acetoacetate) which was obtained by single crystal X-ray diffraction. The study revealed that the β-keto ester groups acted as chelating ligands in all cases and thus polymerizable coordination compounds were formed. However, NMR analyses in solution showed that transesterification of the methacrylic-type monomers occurred even at mild conditions as a side reaction in a ratio which was found to be dependent on the type of metal alkoxide used.
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C Sanchez B Julian P Belleville M Popall (2005) J Mater Chem 15 3559 Occurrence Handle10.1039/b509097k Occurrence Handle1:CAS:528:DC%2BD2MXpsFeitrY%3D
C Sanchez GJ de Soler-Illia F Ribot T Lalot CR Mayer V Cabuil (2001) Chem Mater 13 3061 Occurrence Handle10.1021/cm011061e Occurrence Handle1:CAS:528:DC%2BD3MXnsV2ntbs%3D
G Kickelbick (2002) Progr Polym Sci 28 83 Occurrence Handle10.1016/S0079-6700(02)00019-9
C Sanchez F Ribot (1994) New J Chem 18 1007 Occurrence Handle1:CAS:528:DyaK2cXntVKhurY%3D
Brinker CJ, Scherer GW (1990) Sol-Gel Science: The Physics and Chemistry of Sol–Gel Processing, Academic Press
Schubert U, Huesing N (2004) Synthesis of Inorganic Materials, Wiley-Vch
U Schubert (2005) J Mater Chem 15 3701 Occurrence Handle10.1039/b504269k Occurrence Handle1:CAS:528:DC%2BD2MXpsFeis7g%3D
G Kickelbick U Schubert (2001) Monatsh Chem 132 13 Occurrence Handle1:CAS:528:DC%2BD3MXis1Omur8%3D
C Sanchez B Lebeau F Ribot M In (2000) J Sol-Gel Sci Techn 19 31 Occurrence Handle10.1023/A:1008753919925 Occurrence Handle1:CAS:528:DC%2BD3MXotVyqsw%3D%3D
B Moraru N Huesing G Kickelbick U Schubert P Fratzl H Peterlik (2002) Chem Mater 14 2732 Occurrence Handle10.1021/cm021113f Occurrence Handle1:CAS:528:DC%2BD38Xjs1SntrY%3D
G Kickelbick P Wiede U Schubert (1999) Inorg Chim Acta 284 1 Occurrence Handle10.1016/S0020-1693(98)00251-5 Occurrence Handle1:CAS:528:DyaK1MXkslyhtA%3D%3D
G Kickelbick U Schubert (1997) Chem Ber 130 473 Occurrence Handle1:CAS:528:DyaK2sXitlSltL4%3D
FR Kogler M Jupa M Puchberger U Schubert (2004) J Mater Chem 14 3133 Occurrence Handle10.1039/b405769d Occurrence Handle1:CAS:528:DC%2BD2cXovFGgs7k%3D
Jupa M, Kickelbick G, Schubert U (2004) Europ J Inorg Chem 1835
N Miele-Pajot LG Hubert-Pfalzgraf R Papiernik J Vaissermann R Collier (1999) J Mater Chem 9 3027 Occurrence Handle10.1039/a904491d Occurrence Handle1:CAS:528:DyaK1MXnsF2ntb0%3D
C Barglik-Chory U Schubert (1995) J Sol-Gel Sci Techn 5 135 Occurrence Handle10.1007/BF00487729 Occurrence Handle1:CAS:528:DyaK28XlvFyqsg%3D%3D
J Mendez-Vivar P Bosch VH Lara R Mendoza-Serna (2002) J Sol-Gel Sci Techn 25 249 Occurrence Handle10.1023/A:1020216229397 Occurrence Handle1:CAS:528:DC%2BD38XntVKqtLc%3D
MSM Saifullah D-J Kang KRV Subramanian ME Welland K Yamazaki K Kurihara (2004) J Sol-Gel Sci Techn 29 5 Occurrence Handle10.1023/B:JSST.0000016131.35342.2f Occurrence Handle1:CAS:528:DC%2BD2cXht1CmtbY%3D
U Gbureck J Probst R Thull (2003) J Sol-Gel Sci Techn 27 157 Occurrence Handle10.1023/A:1023746416871 Occurrence Handle1:CAS:528:DC%2BD3sXjslGqsrw%3D
U Patil M Winter H-W Becker A Devi (2003) J Mater Chem 13 2177 Occurrence Handle10.1039/b304419j Occurrence Handle1:CAS:528:DC%2BD3sXmsFWhsr4%3D
Baunemann A, Thomas R, Becker R, Winter M, Fischer RA, Ehrhart P, Waser R, Devi A (2004) J Chem Soc, Chem Commun 1610
R Bhakta R Thomas F Hipler HF Bettinger J Mueller P Ehrhart A Devi (2004) J Mater Chem 14 3231 Occurrence Handle10.1039/b405963h Occurrence Handle1:CAS:528:DC%2BD2cXovFGgsLs%3D
B Corain M Zecca P Mastrorilli S Lora G Palma (1993) Makromol Chem, Rapid Commun 14 799 Occurrence Handle10.1002/marc.1993.030141211 Occurrence Handle1:CAS:528:DyaK2cXjtFensQ%3D%3D
P Mastrorilli CF Nobile GP Suranna MR Taurino M Latronico (2002) Inorg Chim Acta 335 107 Occurrence Handle10.1016/S0020-1693(02)00832-0 Occurrence Handle1:CAS:528:DC%2BD38XksVClt7s%3D
D Hoebbel T Reinert H Schmidt E Arpac (1997) J Sol-Gel Sci Techn 10 115 Occurrence Handle10.1023/A:1018305811088 Occurrence Handle1:CAS:528:DyaK2sXotVSqur0%3D
RJ Errington J Ridland W Clegg RA Coxall JM Sherwood (1998) Polyhedron 17 659 Occurrence Handle10.1016/S0277-5387(97)00418-X Occurrence Handle1:CAS:528:DyaK1cXivV2ns7c%3D
LC Cauro-Gamet LG Hubert-Pfalzgraf S Lecocq (2004) Z Anorg Allg Chem 630 2071 Occurrence Handle10.1002/zaac.200400279 Occurrence Handle1:CAS:528:DC%2BD2cXpslelu70%3D
J Blanchard S Barboux-Doeuef J Maquet C Sanchez (1995) New J Chem 19 929 Occurrence Handle1:CAS:528:DyaK2MXovVOitLY%3D
Seebach D, Hungerbuehler E, Naef R, Schnurrenberger P, Weidmann B, Zueger M (1982) Synthesis 138
Pajot N, Papiernik R, Hubert-Pfalzgraf LG, Vaissermann J, Parraud S (1995) J Chem Soc Chem Commun 1817
Armarego WLF, Perrin DD (1996) Purification of Laboratory Chemicals, Reed Educational and Professional Publishing
Sheldrick GM (1996) In: SADABS (ed) University of Göttingen G
Sheldrick GM (1997) In: SHELXS97 and SHELXL97 (ed) University of Göttingen G
M Sibrian-Vazquez DA Spivak (2003) J Org Chem 68 9604 Occurrence Handle14656084 Occurrence Handle10.1021/jo0352225 Occurrence Handle1:CAS:528:DC%2BD3sXovVOhur0%3D
T Kobayashi T Inoue S Nishino Y Fujihara K Oizumi T Kimura (1995) Chem Pharm Bull 43 797 Occurrence Handle7553967 Occurrence Handle1:CAS:528:DyaK2MXnsVWlsbc%3D
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Ivanovici, S., Puchberger, M., Fric, H. et al. Coordination Behavior of Acetoacetate Ligands with Attached Methacrylate Groups Containing Alkyl-Spacers of Different Length to Titanium and Zirconium Alkoxides. Monatsh. Chem. 138, 529–539 (2007). https://doi.org/10.1007/s00706-007-0632-3
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DOI: https://doi.org/10.1007/s00706-007-0632-3