作者:Roy Buschbeck、Heinrich Lang
DOI:10.1016/j.jorganchem.2004.10.060
日期:2005.3
The synthesis of titanocenedichloride end-grafted carbosiloxane dendrimers of the 1(st) and 2(nd) generation is reported. To find the optimal reaction conditions, Me2ClSiH (1) was reacted with (eta(5)-C5H4SiMe2CH = CH2)(eta(5)-C5H5)TiCl2 (2).The best result could be obtained with the Karstedt catalyst, whereby exclusively the beta-isomer ((eta(5)-C5H4SiMe2CH2CH2SiMe2Cl)(eta(5)-C5H5)TiCl2, 3) is formed. Under similar conditions Me3SiOCH(Me)(CH2)(4)SiMe2H (4) reacts with 2 to give (eta(5)-C5H4SiMe2CH2CH2SiMe2(CH2)(4)CH(Me)OSiMe3)(eta(5) -C5H5)TiCl2 (5). When using MeSi(OCH(Me)(CH2)(4)SiMe2H)(3) (6), Si(OCH(Me)(CH2)(4)SiMeH)(4) (8) and MeSi[O(CH2)(3)SiMe(OCH(Me)(CH2)(4)SiMe2H)(2)](3) (10) instead of I and 4, the respective metallo dendrimers MeSi[OCH(Me)(CH2)(4)SiMe2CH2CH2SiMe2(eta(5) -C5H4)(eta(5)-C5H5)TiC2](3) (7), Si[OCH(Me)(CH2)(4)SiMe2CH2CH2SiMe2(eta(5)-C5H4)(eta(5)-C5H5)TiCl2](4) (9) and MeSiO(CH2)(3)SiMe[OCH(Me)(CH2)(4)SiMe2CH2CH2SiMe2(eta(5)-C5H4)(eta(5)-C5H5)TiCl2](2)}(3) (11) can be isolated.Compounds 3, 5, 7, 9 and 11 were characterised by elemental analysis as well as IR and NMR spectroscopy (H-1, C-13H-1}, Si-29H-1}. (c) 2004 Elsevier B.V. All rights reserved.