1.3-Silylgruppenwanderung im Si2NSiN-Gerüst - Synthese und Molekülstruktur von 1.3-Diaza-2.4-disilacyclobutanen / 1,3-Migration of Silylgroups in the Si2NSiN-System - Synthesis and Molecular Structure of 1,3-Diaza-2,4-disilacyclobutanes

1980 ◽  
Vol 35 (3) ◽  
pp. 275-281 ◽  
Author(s):  
William Clegg ◽  
Uwe Klingebiel ◽  
Cornelia Krampe ◽  
George M. Sheldrick
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Nitrogen Atom ◽  
Structure Determination ◽  
Crystal Structure Determination ◽  
Lithium Salts ◽  
Trimethylsilyl Group ◽  
System Synthesis ◽  
Butyl Lithium

Abstract N-Organylamino-N′,N′-bis(trimethyl)amino-fluoroorganylsilanes react with butyl-lithium to give the corresponding lithium salts. Further reaction of these lithium salts with fluorosilanes leads to the formation of the expected substituted compounds. Diaza-disilacyclobutanes are formed by thermal LiF elimination in THF. The simultaneous 1,3-migration of a trimethylsilyl group from one nitrogen atom to another is demonstrated by the crystal structure determination of the products of two such reactions, with different substituent groups.

scholarly journals Sulfur and Selenium Complexes of the Hydrido-tri(3,5-dimethyl-1-pyrazolyl) borate Nitrosylmolybdenum Fragment, [Tp*Mo(NO)]. An X-Ray Crystal Structure Determination of Tp*Mo(NO)(Se5)

1996 ◽  
Vol 51 (5) ◽  
pp. 681-685 ◽  
Author(s):  
Max Herberhold ◽  
Guo-Xin Jin ◽  
Arnold L. Rheingold
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Mass Spectroscopy ◽  
Structure Determination ◽  
Chair Conformation ◽  
Crystal Structure Determination ◽  
X Ray ◽  
Hydrolysis Of

The reactions of hydrido-tri(3,5-dimethyl-1-pyrazolyl)borate nitrosylmolybdenum diiodide, Tp*Mo(NO)I2 (2), with the oligochalcogenides (NH4)2S10 and (NEt4)2Se6 in THF solution lead to mononuclear cyclo-pentachalcogenido complexes, Tp*Mo(NO)(E5) (E = S (3a), Se (3b)). In the presence of either H2S or H2Se (generated by slow “in situ” hydrolysis of AI2E3 in moist THF solution) 2 is converted into binuclear chalcogenido-bridged products, Tp*2Mo2(NO)2(μ-E)2(E = S (4a), Se (4b)) which are more conveniently obtained from 3a,b by dechalcogenation with tri(″butyl)phosphane (1:4,5). The new chalcogen complexes 3a,b and 4a,b were characterized by IR, NMR and mass spectroscopy and compared with the related chalcogen compounds derived from pentamethylcyclopentadienyl nitrosylmolybdenum diiodide, Cp*Mo(NO)l2. The molecular structure of Tp*Mo(NO)(Se5) (3b) has been determined; the complex contains a sixmembered MoSe5; metallacycle in the chair conformation and a linearly coordinated nitrosyl ligand (angle Mo-N-O 178.9(17)°).

Vom Fluorsilan zum Siloxan — 1,3-Silylgruppenwanderung am Si3CSiO-Gerüst/ From a Fluorosilane to a Siloxane — 1,3-Migration of Silyl Groups in the Si3CSiO System

1985 ◽  
Vol 40 (8) ◽  
pp. 1023-1028 ◽  
Author(s):  
Uwe Klingebiel ◽  
Sabine Pohlmann ◽  
Lutz Skoda ◽  
Cornelia Lensch ◽  
George M. Sheldrick
Keyword(s):  
Crystal Structure ◽  
Structure Determination ◽  
Crystal Structure Determination ◽  
Silyl Groups ◽  
Trimethylsilyl Groups

AbstractThe nature of the products which are formed in the reaction of tris(trimethylsilyl)Methylfluorosilanes (Me3Si)3C -SiF2R with KOH depends on the bulkiness of the substituents R. The condensed siloxane is obtained for R = F . The crystal structure determination of this siloxane (Me3Si)3C -SiF2-O -SiF2-C (SiMe3)3 shows that the Si -O - Si unit is linear. A fluorosilanol as well as a siloxane could be isolated for R = Me. 1,3-Migration of one or two trimethylsilyl groups from the carbon to the oxygen takes place for R = phenyl, rm-butyl or silylamine, with formation of siloxanes which are isomeres o f the expected silanols.

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