Title: On the Gallanyls R*3Ga2· and R*4Ga3· As Well As Gallanides R*3Ga2− and R*4Ga3− (R* = SitBu3) − Syntheses, Characterization, Structures
Abstract: European Journal of Inorganic ChemistryVolume 2001, Issue 7 p. 1719-1727 Full Paper On the Gallanyls R*3Ga2· and R*4Ga3· As Well As Gallanides R*3Ga2− and R*4Ga3− (R* = SitBu3) − Syntheses, Characterization, Structures Nils Wiberg, Nils Wiberg Department Chemie der Universität München, Butenandtstraße 5−13 (Haus D), 81377 München, GermanySearch for more papers by this authorThomas Blank, Thomas Blank Department Chemie der Universität München, Butenandtstraße 5−13 (Haus D), 81377 München, GermanySearch for more papers by this authorKerstin Amelunxen, Kerstin Amelunxen Department Chemie der Universität München, Butenandtstraße 5−13 (Haus D), 81377 München, GermanySearch for more papers by this authorHeinrich Nöth, Heinrich Nöth Department Chemie der Universität München, Butenandtstraße 5−13 (Haus D), 81377 München, GermanySearch for more papers by this authorJörg Knizek, Jörg Knizek Department Chemie der Universität München, Butenandtstraße 5−13 (Haus D), 81377 München, GermanySearch for more papers by this authorTassilo Habereder, Tassilo Habereder Department Chemie der Universität München, Butenandtstraße 5−13 (Haus D), 81377 München, GermanySearch for more papers by this authorWolfgang Kaim, Wolfgang Kaim Institut für Anorganische Chemie der Universität Stuttgart, Plattenwaldring 55, 70550 Stuttgart, GermanySearch for more papers by this authorMatthias Wanner, Matthias Wanner Institut für Anorganische Chemie der Universität Stuttgart, Plattenwaldring 55, 70550 Stuttgart, GermanySearch for more papers by this author Nils Wiberg, Nils Wiberg Department Chemie der Universität München, Butenandtstraße 5−13 (Haus D), 81377 München, GermanySearch for more papers by this authorThomas Blank, Thomas Blank Department Chemie der Universität München, Butenandtstraße 5−13 (Haus D), 81377 München, GermanySearch for more papers by this authorKerstin Amelunxen, Kerstin Amelunxen Department Chemie der Universität München, Butenandtstraße 5−13 (Haus D), 81377 München, GermanySearch for more papers by this authorHeinrich Nöth, Heinrich Nöth Department Chemie der Universität München, Butenandtstraße 5−13 (Haus D), 81377 München, GermanySearch for more papers by this authorJörg Knizek, Jörg Knizek Department Chemie der Universität München, Butenandtstraße 5−13 (Haus D), 81377 München, GermanySearch for more papers by this authorTassilo Habereder, Tassilo Habereder Department Chemie der Universität München, Butenandtstraße 5−13 (Haus D), 81377 München, GermanySearch for more papers by this authorWolfgang Kaim, Wolfgang Kaim Institut für Anorganische Chemie der Universität Stuttgart, Plattenwaldring 55, 70550 Stuttgart, GermanySearch for more papers by this authorMatthias Wanner, Matthias Wanner Institut für Anorganische Chemie der Universität Stuttgart, Plattenwaldring 55, 70550 Stuttgart, GermanySearch for more papers by this author First published: 25 May 2001 https://doi.org/10.1002/1099-0682(200107)2001:7<1719::AID-EJIC1719>3.0.CO;2-QCitations: 39Read the full textAboutPDF 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 The reduction of black-blue tris(supersilyl)digallanyl [R*2Ga−GaR*]· (R* = SitBu3 = supersilyl) in organic solvents with Na, NaC10H8, or NaR* leads to deep-red sodium tris(supersilyl)digallanide−THF(1/3) NaGa2R*3×3THF = [R*2Ga−GaR*Na(THF)3], which transforms in the presence of 18-crown-6 into deep-blue sodium tetrakis(supersilyl)trigallanide−18-crown-6(1/1)−THF(1/2) [Na(18-C-6)(THF)2]+[R*2Ga−GaR*−GaR*]−.The oxidation of the latter anion with R*Br or TCNE as well as the reaction of the digallanyl R*3Ga2· with R*Br leads to deep-green tetra(supersilyl)cyclotrigallanyl [···R*Ga−GaR*2−GaR*···]·. The latter radical thermolizes at 100 °C to dark-violet tetrakis(supersilyl)-tetrahedro-tetragallane R*4Ga4 besides the digallanyl R*3Ga2·. This is also prepared from NaR* and GaCl3 or R*2GaCl, as well as by oxidation of R*3Ga2−, and itself thermolizes with formation of the tetrahedrane R*4Ga4. According to X-ray structure analyses of the mentioned compounds, the Ga−Ga bond of the digallanide NaGa2R*3×3THF (NMR spectroscopically observed) is comparably short (2.380 Å), approaching a bond order of 2. In fact, it is distinctly shorter than the Ga−Ga bond (2.420 Å) in the digallanyl R*3Ga2· (EPR spectroscopically observed). The Ga atoms of the trigallanyl R*4Ga3· (EPR spectroscopically observed) are located at the corners of a triangle with two shorter R*2Ga−GaR* sides (2.527 Å) and a comparably longer R*Ga−GaR* basis (2.879 Å). The mean value of the two Ga−Ga bonds in the trigallanide R*4Ga3− (NMR spectroscopically observed) is as long (2.53 Å) as the short Ga−Ga bonds in R*4Ga3·. The anion shows an intramolecular CH3···Ga contact (C−Ga 2.10 Å) between one peripheral methyl group of the R*2Ga entity and the anionic Ga atom in [R*2Ga−GaR*−GaR*]−. Citing Literature Volume2001, Issue7July 2001Pages 1719-1727 RelatedInformation
Publication Year: 2001
Publication Date: 2001-07-01
Language: en
Type: article
Indexed In: ['crossref']
Access and Citation
Cited By Count: 42
AI Researcher Chatbot
Get quick answers to your questions about the article from our AI researcher chatbot