title: Synthesis of metallasiloxanes of group 13-15 and their application in catalysis.
abstract: 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.
authors.affiliation: State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, China.
authors.forename: Yan
authors.initials: Y
authors.lastname: Li
authors.forename: Jinjin
authors.initials: J
authors.lastname: Wang
authors.forename: Yile
authors.initials: Y
authors.lastname: Wu
authors.forename: Hongping
authors.initials: H
authors.lastname: Zhu
authors.forename: Prinson P
authors.initials: PP
authors.lastname: Samuel
authors.forename: Herbert W
authors.initials: HW
authors.lastname: Roesky
mesh_terms: D002384:Catalysis; D019216:Metals, Heavy / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D012833:Siloxanes / Q000737:chemistry*
chemical_list: D019216:Metals, Heavy; D009942:Organometallic Compounds; D012833:Siloxanes