Tetrylenes chelated by hybrid amido-amino ligand: derivatives of 2-[(N,N-dimethylamino)methyl]aniline
| Autor: | Jan Turek, Zdeňka Padělková, Frank De Proft, Hana Vaňkátová, Aleš Růžička, Lies Broeckaert, Roman Olejník |
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| Přispěvatelé: | General Chemistry, Chemistry |
| Rok vydání: | 2011 |
| Předmět: |
STRUCTURAL-CHARACTERIZATION
MAIN-GROUP ELEMENTS Trimethylsilyl Chemistry Stereochemistry Ligand VALENT GROUP-14 1 3-DIMETALLACYCLOBUTANES MOLECULAR CALCULATIONS Medicinal chemistry EFFECTIVE CORE POTENTIALS Inorganic Chemistry DENSITY-FUNCTIONAL THEORY Transmetalation chemistry.chemical_compound N-HETEROCYCLIC GERMYLENES ELECTRONIC-STRUCTURE Deprotonation Aniline Amide Butyllithium Moiety Physical and Theoretical Chemistry COORDINATION CHEMISTRY TIN(II) COMPLEXES |
| Zdroj: | Vrije Universiteit Brussel |
| ISSN: | 1520-510X |
| Popis: | Reaction of 2-[(dimethylamino)methyl]aniline with butyllithium, followed by conversion with triinethylsilyl, triphenylsilyl, triphenylgermyl, trimethylstannyl, or tri-n-butyl-stannyl chloride, gives the corresponding substituted aniline. These compounds were further deprotonated by butyllithium and reacted with germanium, tin, and lead dichlorides, respectively, in both stoichiometric ratios 2:1 and 1:1, providing the target homo- ([2-(Me(2)NCH(2))C(6)H(4)(YR(3))N](2)M) and heteroleptic ([2-(Me(2)NCH(2))C(6)H(4)(YR(3))N]MCl) germylenes and stannylenes, where M = Ge, Sn, Y = Si, Ge, and R = Me, Ph. Unlike all of these cases, the heteroleptic plumbylene can only be obtained with this reaction when the amide is substituted by a trimethylsilyl moiety. Anilines substituted by trimethyltin or tri-n-butyltin moieties gave transmetalation products after the second deprotonation by butyllithium. The trimethyltin-substituted stannylenes could likewise not be obtained by hexamethyldisilazane elimination of (trimethylstannyl)-2-[(dimethylamino)methyl]aniline with 0.5 mol equiv of either bis[bis(trimethylsilyl)amido]tin or bis[bis(trimethylsilyl)amido]tin chloride}. Products of these reactions are heterocubanes with compositions {[2-(Me(2)NCH(2))C(6)H(4)N]Sn}(4) and [2-(Me(2)NCH(2))C(6)H(4)N](2)-(mu(2)-SnMe(2))(2), respectively, and Me(4)Sn or Me(3)SnCl. The structures of trimethylsilyl- and triphenylgermyl-substituted germylenes, stannylenes, and plumbylenes, as well as a number of their precursors, in the crystalline state, were investigated by X-ray diffraction and NMR spectroscopy in solution. Density functional theory methods were used for evaluation of the structures of several compounds. |
| Databáze: | OpenAIRE |
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