@article{TackeWiesenbergerBeckeretal.1992, author = {Tacke, Reinhold and Wiesenberger, F. and Becker, B. and Rohr-Aehle, R. and Schneider, P. B. and Ulbrich, U. and Sarge, S. M. and Cammenga, H. K. and Koslowski, T. and Niessen, W. von}, title = {Ester von (Hydroxymethyl)diorganylsilanen: Synthese und thermisch induzierte Umlagerung}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-64188}, year = {1992}, abstract = {Twenty silanes of the type R\(^1\)R\(^2\)Si(H)CH\(_2\)OR\(^3\) (A) were syn- and entropy of activation) of these reactions were studied by thesized {R\(^1\), R\(^2\) = Me, Ph, 1-naphthyl, PhCH\(_2\), Me\(_3\)SiCH\(_2\); OR\(^3\) means of d{\"u}ferential scanning calorimetry (DSC). In addition, = OC(O)Me, OC(O)Ph, OC(O)CF\(_3\) , OS(0)\(_2\)CF\(_3\), OP(O)Ph\(_2\), the kinetics of all reactions were investigated by 1H-NMR OC(O)Cl, and studied for their thermal behaviour. The silanes spectroscopy. The transition state of the rearrangement was A undergo a thermally induced rearrangement to give the investigated by an ab initio study based on the model comcorresponding silanes R\(^1\)R\(^2\)Si(OR\(^3\))Me (B). For compounds with pound H\(_3\)SiCH\(_2\)OC(O)H (-> MeH\(_2\)SiOC(O)H]. The theoretical OR3 = OC(O)Cl, an additional decarboxylation takes place to data and the experimentally obtained energetic and kinetic yield the chlorosilanes R1R2Si(Cl)Me. Except for the deriva- data are discussed in terms of mechanistic aspects of the retives with OR\(^3\) = OC(O)Cl, the energetic (reaction enthalpy) arrangement reaction A -> B. and kinetic data (reaction order, frequency factor, enthalpy ...}, subject = {Anorganische Chemie}, language = {de} } @article{TackeSperlichBecker1994, author = {Tacke, Reinhold and Sperlich, J. and Becker, B.}, title = {Bis[2,3-naphthalenediolato(2-)](pyrrolidinio-methyl)germanate-tetartoacetonitrile, the first zwitterionic \(\lambda_5\)-germanate: synthesis and crystal structure analysis}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-64329}, year = {1994}, abstract = {The zwitterionic spirocyclic \(\lambda_5\)-germanate bis(2,3-naphthalenediolato( 2-)](pyrrolidiniomethyl)germanate (8) was synthesized and the crystal structure of its tetartoacetonitrile solvate 8 · 1/4 CH\(_3\)CN studied by single-crystal X-ray diffraction. Compound 8 was prepared by reaction of (MeO)\(_3\)GeCH\(_2\)NC\(_4\)H\(_8\) (11; NC\(_4\)H\(_8\) = pyrrolidino) with two equivalents of 2,3-naphthalenediol (isolated as 8 · 1/4 CH\(_3\)CN; yield 92\%). The coordination polyhedron around the pentacoordi- naphthalenediolatonate germanium atom of 8 · 1/4 CH\(_3\)CN can be described as a strongly distorted trigonal bipyramid (the structure is displaced by 38.9\% from the ideal trigonal bipyrarnid towards the ideal square pyramid), the carbon atom occupying an equatorial position. In the crystal lattice of 8 · 1/4 CH\(_3\)CN, the zwitterions form intermolecular N-H ... o hydrogen bonds leading to the formation of dimers. 1H- and \(^{13}\C-NMR studies revealed that 8 also exists in solution ([D\(_6\)]DMSO).}, subject = {Anorganische Chemie}, language = {en} } @article{TackeBeckerLange1990, author = {Tacke, Reinhold and Becker, B. and Lange, H.}, title = {(Thioacetoxy-S-methyl)diorganylsilane und (Mercaptomethyl)diorganylsilane: Synthese und Eigenschaften}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-64065}, year = {1990}, abstract = {Die erstmalige Synthese der (Thioacetoxy-S-methyl)diorganylsilane (CH\(_3\))\(_2\)Si(H)CH\(_2\)SC(O)CH\(_3\) (9) und (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)SC(O)CH\(_3\) (10) und der (Mercaptomethyl) diorganylsilane (CH\(_3\))\(_2\)Si(H)CH\(_2\)SH (11) und (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)SH (12) wird beschrieben. W{\"a}hrend sich die Silane 9 und 10 leicht handhaben lassen, neigen die strukturanalogen (Hydroxymethyl)diorganylsilane (CH\(_3\))\(_2\)Si(H)CH\(_2\)OH (1) und (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)OH (2) zu einer basenkatalysierten Zersetzung (Bildung oligomerer (polymerer) Alkoxysilane und Wasserstoff). Im Gegensatz zu den thermisch labilen (Acetoxymethyl)diorganylsilanen (CH\(_3\))\(_2\)Si(H)CH\(_2\)OC(O)CH\(_3\) (3) und (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)OC(O)CH\(_3\) (4) (--+ Umlagerung zu den entsprechenden Acetoxy(methyl) diorganylsilanen (CH\(_3\)) \(_3\)SiOC(O)CH\(_3\) (5) und CH\(_3\)(C\(_6\)H\(_5\))\(_2\)SiOC(O)CH\(_3\) {6)) sind die Thio-Analoga 9 und 10 thermisch stabil (I-molare L{\"o}sungen in C\(_6\)D\(_6\), 30 h bei 180 o C).}, subject = {Anorganische Chemie}, language = {de} } @article{TackeBeckerBergetal.1992, author = {Tacke, Reinhold and Becker, B. and Berg, D. and Brandes, W. and Dutzmann, S. and Schaller, S.}, title = {Bis(4-fluorophenyl)methyl(1H-1,2,4-triazol-1-yl-methyl)germane, a germanium analogue of the agricultural fungicide flusilazole: synthesis and biological properties}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-64224}, year = {1992}, abstract = {Bis( 4-fluorophenyl)methyl(l H-1,2,4-triazol-1-yl-methyl)germane (2), a germanium analogue of the agricultural fungicide flusilazole (1), has been synthesized from Cl\(_3\)GeCH\(_2\)CI (3) by both a three-step and a four-step synthesis (3-> (p-F-C\(_6\)H\(_4\))\(_2\)Ge(CH\(_2\)Cl)Br (4)-> (p-F-C\(_6\)H\(_4\))\(_2\)Ge(CH\(_2\)CI)CH\(_3\) (S)-> 2; S ~ (p-F-C\(_6\)H\(_4\))\(_2\)Ge(CH\(_2\)I)CH\(_3\) (6)-> l). The fungicidal properties of l have been compared with those of the parent silicon compound 1 (studies on Si/Ge bioisosterism). In various test systems, the SijGe analogues 1 and 2 showed comparable fungicidal properlies (in activity against plant pathogenic fungi: in agar plate diffusion tests and greenhause evaluations; in activity against human pathogenic fungi: in serial dilution tests). In addition, 1 and 2 displayed comparable potencies in respect of sterol biosynthesis inhibition in Sacclulromycopsis {\"u}polytica and Pyricularia oryzae, the mode of action being primarily an inhtbition of oxidative C14-demethylation.}, subject = {Anorganische Chemie}, language = {en} } @article{TackeBecker1988, author = {Tacke, Reinhold and Becker, B.}, title = {Synthese und Eigenschaften von (Hydroxymethyl)dimethylgerman und (Hydroxymethyl)diphenylgerman}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-63895}, year = {1988}, abstract = {Die (Hydroxymethyl)diorganylgermane (CH\(_3\))\(_2\)Ge(H)CH\(_2\)OH und (C\(_6\)H\(_5\))\(_2\)Ge(H)CH\(_2\)OH wurden - ausgehend von GeCl\(_4\) - durch eine jeweils vierstufige Synthese mit einer Gesamtausbeute von 15 bzw. 32\% dargestellt (GeCl\(_4\) ---+ Cl\(_3\)GeCH\(_2\)Cl -> R \(_2\)Ge(Cl)CH \(_2\)Cl ->R \(_2\)Ge(OAc)CH\(_2\)OAc--) R \(_2\)Ge(H)CH\(_2\)OH; R = CH\(_3\) bzw. C\(_6\)H\(_5\) ). Die chemische Reaktivit{\"a}t der Germane (CH\(_3\))\(_2\)Ge(H)CH\(_2\)OH und (C\(_6\)H\(_5\))\(_2\)Ge(H)CH\(_2\)OH wird durch deren Ge-H- und 0-H-Bindung bestimmt.}, subject = {Anorganische Chemie}, language = {de} } @article{SargeCammengaBeckeretal.1988, author = {Sarge, S. and Cammenga, H. K. and Becker, B. and Rohr-Aehle, R. and Tacke, Reinhold}, title = {Energetic and kinetic investigation of thermally induced molecular rearrangements of esters of (hydroxymethyl)hydridosilanes by DSC}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-63850}, year = {1988}, abstract = {No abstract available}, subject = {Anorganische Chemie}, language = {en} }