Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 573, CZ - 532 10, Pardubice, Czech Republic.
Dalton Trans. 2013 Dec 14;42(46):16403-11. doi: 10.1039/c3dt52230j.
The reaction of an N,C,N-intramolecularly coordinated tin(IV) carbonate LSn(Ph)(CO3) (1) and antimony(III) and bismuth(III) oxides (LMO)2 (where M = Sb (2), Bi (3) and L = C6H3-2,6-(CH2NMe2)2) with (HO)SiPh2(O)SiPh2(OH) in 1 : 1 (in the case of 1) or 1 : 2 molar ratio (in the cases of 2 and 3) gave the metallasiloxanes cyclo-LSn(Ph)(OSiPh2)2O (4) and cyclo-LM(OSiPh2)2O (where M = Sb (6) and Bi (7)) containing six-membered MSi2O3 rings. Alternatively, the compounds 4, 6 and 7 can be also prepared reacting Ph2Si(OH)2 and compounds 1, 2 and 3, respectively, in the molar ratio of either 2 : 1 (for 4) or 4 : 1 (for 6 and 7). The reaction of Ph2Si(OH)2 with 1 in 1 : 1 molar ratio gave cyclo-Ph2Si(OSnL(Ph)O)2SiPh2 (5) containing an eight-membered Sn2Si2O4 stannasiloxane ring. The analogous eight-membered stibasiloxane derivative cyclo-Ph2Si(OSbLO)2SiPh2 (8) was obtained as well, while attempts to synthesize the bismuth analogue failed. Compounds 1-3 react with the siloxane cyclo-(Me2SiO)3 providing either eight-membered metallasiloxanes cyclo-LSn(Ph)(OSiMe2O)2SiMe2 (9) and cyclo-LSb(OSiMe2O)2SiMe2 (10) or the six-membered bismutasiloxane cyclo-LBi(OSiMe2)2O (11). All compounds were characterized with the help of elemental analysis, (1)H, (13)C, (29)Si and (119)Sn NMR spectroscopy, and single crystal X-ray diffraction analyses (except 9 and 10).
锡(IV)碳酸盐 LSn(Ph)(CO3)（1）与锑(III)和铋(III)氧化物（LMO）2（其中 M = Sb（2），Bi（3）和 L = C6H3-2,6-(CH2NMe2)2）在 1：1（对于 1）或 1：2 摩尔比（对于 2 和 3）的条件下发生反应，得到了六元 MSi2O3 环的金属硅氧烷环己基-LSn(Ph)(OSiPh2)2O（4）和环己基-LM(OSiPh2)2O（其中 M = Sb（6）和 Bi（7））。或者，化合物 4、6 和 7 也可以通过 Ph2Si(OH)2 与化合物 1、2 和 3 以 2：1（对于 4）或 4：1（对于 6 和 7）的摩尔比反应制备。Ph2Si(OH)2 与 1 以 1：1 摩尔比反应得到含有八元 Sn2Si2O4 锡硅氧烷环的环己基-Ph2Si(OSnL(Ph)O)2SiPh2（5）。同样获得了类似的八元锑硅氧烷衍生物环己基-Ph2Si(OSbLO)2SiPh2（8），而合成铋类似物的尝试失败了。化合物 1-3 与硅氧烷环己基-(Me2SiO)3 反应，提供了八元金属硅氧烷环己基-LSn(Ph)(OSiMe2O)2SiMe2（9）和环己基-LSb(OSiMe2O)2SiMe2（10）或六元铋硅氧烷环己基-LBi(OSiMe2)2O（11）。所有化合物均通过元素分析、（1）H、（13）C、（29）Si 和（119）Sn NMR 光谱以及单晶 X 射线衍射分析（9 和 10 除外）进行了表征。
