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Synthesis and Structure of Siloxy-Substituted ZnO Aggregates Having (ZnO)n (n = 2, 4) and Zn3O4 Cores

2000; Wiley; Volume: 2000; Issue: 12 Linguagem: Inglês

10.1002/1099-0682(200012)2000

1099-0682

Matthias Drieß, Klaus Merz, S. Rell,

Polyoxometalates: Synthesis and Applications

European Journal of Inorganic ChemistryVolume 2000, Issue 12 p. 2517-2522 Full Paper Synthesis and Structure of Siloxy-Substituted ZnO Aggregates Having (ZnO)n (n = 2, 4) and Zn3O4 Cores Matthias Driess, Matthias Driess matthias.driess@ac1.ruhr-uni-bochum.de Lehrstuhl für Anorganische Chemie I: Molekül- und Koordinationschemie, Ruhr-Universität Bochum, Universitätsstra�e 150, 44780 Bochum, Germany, Fax: (internat.) + 49-(0)234/3214378Search for more papers by this authorKlaus Merz, Klaus Merz Lehrstuhl für Anorganische Chemie I: Molekül- und Koordinationschemie, Ruhr-Universität Bochum, Universitätsstra�e 150, 44780 Bochum, Germany, Fax: (internat.) + 49-(0)234/3214378Search for more papers by this authorStefan Rell, Stefan Rell Lehrstuhl für Anorganische Chemie I: Molekül- und Koordinationschemie, Ruhr-Universität Bochum, Universitätsstra�e 150, 44780 Bochum, Germany, Fax: (internat.) + 49-(0)234/3214378Search for more papers by this author Matthias Driess, Matthias Driess matthias.driess@ac1.ruhr-uni-bochum.de Lehrstuhl für Anorganische Chemie I: Molekül- und Koordinationschemie, Ruhr-Universität Bochum, Universitätsstra�e 150, 44780 Bochum, Germany, Fax: (internat.) + 49-(0)234/3214378Search for more papers by this authorKlaus Merz, Klaus Merz Lehrstuhl für Anorganische Chemie I: Molekül- und Koordinationschemie, Ruhr-Universität Bochum, Universitätsstra�e 150, 44780 Bochum, Germany, Fax: (internat.) + 49-(0)234/3214378Search for more papers by this authorStefan Rell, Stefan Rell Lehrstuhl für Anorganische Chemie I: Molekül- und Koordinationschemie, Ruhr-Universität Bochum, Universitätsstra�e 150, 44780 Bochum, Germany, Fax: (internat.) + 49-(0)234/3214378Search for more papers by this author First published: 14 November 2000 https://doi.org/10.1002/1099-0682(200012)2000:12 3.0.CO;2-VCitations: 59AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Abstract Convenient syntheses and X-ray crystallographic characterizations of the first bis(trimethylsilyl)amido-, methyl-, and iodozinc triorganosiloxide aggregates 1−5 are described. They are accessible by the simple reaction of ZnR′2 [R = Me, N(SiMe3)2] with the respective silanols R3SiOH (R = Me, Et, iPr), which affords the dimeric [(Me3Si)2NZnOSiR3]2 (1a: R = iPr; 1b: R = Et), trinuclear [(MeZn)2Zn(OSiiPr3)4] (2a), {[(Me3Si)2NZn]2Zn(OSiR3)4} (2b: R = Et; 2c: R = Me), and tetranuclear heterocubanes [MeZnOSiR3]4 (3a: R = Me; 3b: R = Et), respectively. The latter were oxidized with four equivalents of elemental iodine to form the tetraiodo derivatives [IZnOSiR3]4 (4a: R = Me; 4b: R = Et) in 82 and 88% yield, respectively. Due to the higher polarity of the Zn−I vs. Zn−C σ-bond, the Zn−O distances of the almost regular Zn4O4 core in 4a are 2−6 pm shorter than those observed in the less Lewis-acidic cluster 3b. However, the Zn−O distances in 3b and 4a are ca. 10−15 pm longer than those in 1a, 2a, and 2c, due to different coordination numbers at Zn and the effects of ring strain. Remarkably, the iodo derivatives 4a,b undergo dissociation in THF to give the respective dimeric THF solvates [IZn(THF)OSiR3]2 (5a: R = Me; 5b: R = Et), whereas the Zn4O4 cores in 3a and 3b are retained even in aprotic polar solvents. Citing Literature Volume2000, Issue12December 2000Pages 2517-2522 RelatedInformation