Synthesis and Reactivity of Low Valent Group 13 and 14 (semi)metal Complexes PDF Download
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Languages : en
Pages : 316
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Author:
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Languages : en
Pages : 316
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Author: Xiaofei Sun
Publisher: Cuvillier Verlag
ISBN: 3736966628
Category : Science
Languages : en
Pages : 259
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Die Dissertation befasst sich mit der Anwendung von niedervalenten Gruppe-14-Verbindungen in metallorganischer Chemie und Hauptgruppenchemie. Ausgehend von mono- und divalenten Siliziumverbindungen wurde die analoge Siliziumverbindung des 2π-Hückel-aromatischen Verbindung dargestellt (Kapitel 3.1). Ein chirales Silen wurde synthetisiert und weitere Reaktivität mit unterschiedlichen kleinen Molekülen untersucht (Kapitel 3.2). Außerdem wurden bidentate Silylene als Liganden zur Stabilisierung von Seldenerdelementen, Erdalkalielementen und Gruppe-12-Metallen eingesetzt (Kapitel 3.3-3.4). Verschiedene Polyphosphide wurden aus reduzierenden Silylenen oder Plumbolen generiert (Kapitel 3.5-3.6). Die dianionischen Gruppe-14-Metallole, Silol, Germol und Plumbol wurden als Liganden für sandwichartige Lanthanidkomplexe eingesetzt und die magnetischen Eigenschaften der Er-Verbindung wurden untersucht (Kapitel 3.7-3.8).
Author: Terry Chu
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Languages : en
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Author: Clément René Paul Millet
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Languages : en
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Author: Baixin Qian
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Category : Aluminum compounds
Languages : en
Pages : 362
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Author: Anukul Jana
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Languages : en
Pages : 131
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Author: B. Peerless
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Languages : en
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Author: C. E. Gidman
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Languages : en
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Author: Madison Louis McCrea-Hendrick
Publisher:
ISBN: 9780438627642
Category :
Languages : en
Pages :
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This dissertation describes the synthesis, characterization and reactivity of some low-coordinate, low-oxidation state heavier main group 13 and 14 element species. Chapter 2 describes the reactivity of the heavier main group 13 element digallene, (GaAr[superscript iPr4])2, (Ar[superscript iPr4] = -C6H3-2,6-(C6H3-2,6-[superscript i]Pr2)2) with group 6 transition metal hexacarbonyls under photoirradiation to form the bis(gallanediyl) complexes, trans-bis(GaAr[superscript iPr4])2M(CO)4 (M = Cr, Mo, or W). The mechanism of formation of these products was investigated both computationally and experimentally. A postulated intermediate in their formation is the monogallanediyl complex, Ga(Ar[superscript iPr4])Mo(CO)5 which was synthesized by the reaction (GaAr[superscript iPr4])2 with two equivalents Mo(CO)5NMe3. (GaAr[superscript iPr4])2 was also reacted at 25°C with Co2(CO)8 to give Ga(Ar[superscript iPr4])Co2(CO)7, in which the gallanediyl fragment is bound to each cobalt atom in a bridging fashion. Chapter 3 is an extension of the work in Chapter 2 to the reactions of the heavier main group 14 element dimetallynes, (EAr[superscript iPr4])2 (E = Ge or Sn), with group 6 transition metal hexacarbonyls under photoirradiative conditions. These reactions afforded the products {Ar[superscript iPr4]EM(CO)4}2 (E = Ge or Sn; M = Cr, Mo, or W) which featured rhomboid E2M2 cores with Ar[superscript iPr4]E units bridging transition metal tetracarbonyl fragments, M(CO)4. Chapter 4 describes the reactions of the aryl tin(II) hydrides {Ar[superscript iPr6]Sn([mu]-H)}2 (Ar[superscript iPr6] = C6H3-2,6-(C6H2-2,4,6-[superscript i]Pr6)2) and {Ar[superscript iPr4]Sn([mu]-H)}2 with phenyl acetylene and diphenyl acetylene. The reactions with diphenyl acetylene affords simple insertion of the Sn-H bond into a [pi]-bond of the alkyne to yield the products ArSnC(Ph)C(H)Ph (Ar = Ar[superscript iPr6] or Ar[superscript iPr4]). In contrast, the reaction of {ArSn([mu]-H)}2 with phenyl acetylene affords different products that are connected with the presence (Ar[superscript iPr6]) or absence (Ar[superscript iPr4]) of an isopropyl group at the remote para position of the flanking aryl rings of the terphenyl substituent. When {Ar[superscript iPr6]Sn([mu]-H)}2 is reacted with phenyl acetylene the product Ar[superscript iPr6](H)SnC(H)C(Ph)Sn(H)Ar[superscript iPr6] containing a 1,2-distannacyclobut-3-ene moiety is obtained as a colorless solid. In contrast, the reaction of {Ar[superscript iPr4]Sn([mu]-H)}2 with phenyl acetylene affords a red product of formula Ar[superscript iPr4]SnC(H)C(Ph)Sn(H)2Ar[superscript iPr4] with the tin atoms having different oxidation states of +2 and +4 as determined by solution 119Sn NMR spectroscopy. Chapter 5 describes the synthesis and characterization of the most sterically congested tetrylenes currently known: E(Ar[superscript iPr6])2 (E = Ge, Sn, or Pb). Computational studies of these tetrylenes and E(Ar[superscript Me6])2 (Ar[superscript Me6] = C6H3-2,6-(C6H2-2,4,6-Me3)2) and E(Ar[superscript iPr4])2 were also performed with and without dispersion corrections to evaluate the contribution of London dispersion force effects on the C[subscript ipso]-E-C[subscript ipso] interligand angle.
