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Judith Baumgartner

Publications and source records attributed to Judith Baumgartner.

8 recordsLinked to original sources

Structurally and conformationally defined small methyl polysilanes.

Possessing the property of sigma-bond electron delocalisation, polysilanes are a class of compounds with unique properties. In recent years major progress has been achieved in the theoretical understanding and the synthesis of polysilanes. Much insight into the connection between conformation and electronic properties has been gained from studies of defined small polysilane molecules. The transition from Wurtz type coupling reactions to the stepwise construction of polysilane molecules employing silyl anions as key intermediates has permitted access to defined compounds with a higher degree of structural complexity. Besides this, several methods have been developed to control the conformational properties and thus gain control over the electronic properties of polysilanes.

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Synthesis and structure of sila-adamantane.

An organosilicon cage compound containing the sila-adamantane structural unit, which is the building block of crystalline silicon, was synthesized by the Lewis acid-catalyzed rearrangement reaction of a structural isomer.

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Synthesis of a hafnocene disilene complex.

Reaction of the magnesium transmetalation product of a 1,2-dipotassiodisilane with hafnocene dichloride gives a disilene hafnocene complex. X-ray crystallography of the respective trimethylphosphane adduct provides structural proof for this assignment.

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Open, cyclic, and bicyclic compounds of double silylated phosphorus and boron.

Salt elimination reactions of tris(trimethylsilyl)silyl potassium (1), and two 1,4-dipotassiooligosilanes (3, 5) with 2,2,6,6-tetramethylpiperidinodichloroborane and diethylaminodichlorophosphane have generated open (2), cyclic (4) and bicyclic (6) bora- and phosphaoligosilanes. A monosilylated phosphane and the two five-membered cyclosilanes have been subjected to single crystal X-ray diffraction analysis.

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Adamantanes, nortricyclenes, and dendrimers with extended silicon backbones.

By reaction of the hexabromoheptasilane MeSi(SiMe(2)SiMeBr(2))(3) (1 a) with H(2)O, H(2)S, NH(3), and H(2)NMe the heptasilaadamantanes MeSi(SiMe(2)SiMeO)(3) (4), MeSi(SiMe(2)SiMeS)(3) (5), MeSi(SiMe(2)SiMeNH)(3) (6 a), and MeSi(SiMe(2)SiMeNMe)(3) (6 b), respectively, were prepared in good to moderate yields. Molecular structures of 4, 5, 6 a, and 6 b were determined by X-ray crystallography. The symmetry of the cages is approximately C(3v), and the geometry around the nitrogen atoms is essentially planar. Ab initio SCF/HF calculations with the 6-31G* basis set confirm these results. Reduction of MeSi(SiMe(2)SitBuBr(2))(3) (1 b) with lithium naphthalenide afforded the heptasilanortricyclene MeSi(SiMe(2)SitBu)(3) (7). The (29)Si NMR spectrum of 7 consists of three signals with chemical shifts that agree closely with values predicted by ab initio calculations. (29)Si INADEQUATE spectra also strongly support the nortricyclene structure. Ab initio SCF/HF calculations were performed for the parent molecule Si(7)H(10), and the ring strain of the cage was estimated as 168.8 kJ mol(-1) by using the homodesmic reaction Si(7)H(10) + 3 Si(2)H(6)-->Si(13)H(28). Compound 1 a also served as the starting material for the preparation of first-generation dendrimer 2 a by reaction with six equivalents of Ph(2)MeSiLi. Subsequent protodearylation with HBr and reaction with (Me(2)PhSi)(2)SiMeK afforded second-generation dendrimer 3. All dendrimers were characterized by multinuclear NMR spectroscopy.

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The first stable beta-fluorosilylanion.

The reaction of 2 equiv of tris(trimethylsilyl)silylfluoride with potassium tert-butoxide in the presence of donor molecules (THF, DME, 18-crown-6) leads to the clean formation of an adduct of 1-potassio-2-fluorotetrakis(trimethylsilyl)disilane. Attempts to transmetalate this compound effect the elimination of metal fluoride accompanied by the formation of tetrakis(trimethylsilyl)disilene. The latter can either be trapped in a cycloaddition reaction or in the absence of trapping reagents dimerizes to octakis(trimethylsilyl)cyclotetrasilane.

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