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Synthesis of metallasiloxanes of group 13-15 and their application in catalysis.
|Title||Synthesis of metallasiloxanes of group 13-15 and their application in catalysis.|
|Publication Type||Journal Article|
|Year of Publication||2013|
|Authors||Li Y, Wang J, Wu Y, Zhu H, Samuel PP, Roesky HW|
|Journal||Dalton transactions (Cambridge, England : 2003)|
|Date Published||2013 Oct 7|
Herein we report on the synthesis, characterization and catalytic application of metallasiloxanes of group 13-15. Reactions of R(Me)Si(OH)2 (R = N(SiMe3)-2,6-iPr2C6H3) (A) with Bi(NEt2)3, Sb(NEt2)3, Ge[N(SiMe3)2]2 and AlMe3 afforded [R(Me)SiO2BiNEt2]2 (1), [R(Me)SiO2SbOSi(OH)(Me)R]2 (2), [R(Me)SiO2]3(GeH)2 (3), and [R(Me)SiO2AlMe(THF)]2 (4), respectively. Reactions of RSi(OH)3 (B) with Bi(NEt2)3 and AlMe3 produced complexes (RSiO3Bi)4 (5) and (RSiO3)2[AlMe(THF)]3 (6). Compounds 1-6 have been characterized by IR and NMR spectroscopy, single crystal X-ray structure and elemental analysis. Each of the compounds 1, 2 and 4 features an eight-membered ring of composition Si2O4Bi2, Si2O4Sb2 and Si2O4Al2, while 3 and 6 exhibit a bicyclic structure with the respective skeletons of Si3O6Ge2 and Si2O6Al3. Compound 5 has a cubic core of Si4O12Bi4. Compounds 1-6 exhibit very good catalytic activity in the addition reaction of trimethylsilyl cyanide (TMSCN) with benzaldehyde. Compound 5 was found to be the best catalyst and its activity was probed in the reactions of TMSCN with a number of aldehydes and ketones.
|Alternate Journal||Dalton Trans|