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Popowski, Eckhard; Rietz, Ildiko; Fischer, Christian; Erben, Siegfried; Harloff, Jörg; Reinke, Helmut

Reaktionen von Bis(trimethylsilyl)aminochlorsilanen mit Lithium – N, Si‐Trimethylsilylgruppenwanderung oder Selbstkondensation von Bis(trimethylsilyl)aminosilyllithiumverbindungen

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  • Medientyp: E-Artikel
  • Titel: Reaktionen von Bis(trimethylsilyl)aminochlorsilanen mit Lithium – N, Si‐Trimethylsilylgruppenwanderung oder Selbstkondensation von Bis(trimethylsilyl)aminosilyllithiumverbindungen
  • Beteiligte: Popowski, Eckhard; Rietz, Ildiko; Fischer, Christian; Erben, Siegfried; Harloff, Jörg; Reinke, Helmut
  • Erschienen: Wiley, 2012
  • Erschienen in: Zeitschrift für anorganische und allgemeine Chemie
  • Sprache: Deutsch
  • DOI: 10.1002/zaac.201200081
  • ISSN: 0044-2313; 1521-3749
  • Schlagwörter: Inorganic Chemistry
  • Entstehung:
  • Anmerkungen:
  • Beschreibung: <jats:title>Abstract</jats:title><jats:p>The chlorosilanes [(Me<jats:sub>3</jats:sub>Si)<jats:sub>2</jats:sub>N]HMeSiCl (<jats:bold>1</jats:bold>), [(Me<jats:sub>3</jats:sub>Si)<jats:sub>2</jats:sub>N]<jats:sub>2</jats:sub>MeSiCl (<jats:bold>2</jats:bold>) and [(Me<jats:sub>3</jats:sub>Si)<jats:sub>2</jats:sub>N]RPhSiCl (<jats:bold>3</jats:bold>: R = Me, <jats:bold>4</jats:bold>: R = Ph, <jats:bold>5</jats:bold>: R = (Me<jats:sub>3</jats:sub>Si)<jats:sub>2</jats:sub>N, <jats:bold>6</jats:bold>: R = H) were allowed to react with lithium metal in tetrahydrofuran (THF) or in a mixture of THF/Et<jats:sub>2</jats:sub>O/<jats:italic>n</jats:italic>‐pentane in the volume ratio 4:1:1 (Trapp mixture). <jats:bold>1</jats:bold> and <jats:bold>2 </jats:bold>did not react with lithium in THF at room temperature. A mixture of <jats:bold>1</jats:bold> and Me<jats:sub>3</jats:sub>SiCl in molar ratio 1:1 reacted with lithium to give [(Me<jats:sub>3</jats:sub>Si)<jats:sub>2</jats:sub>N]HMeSi–SiMeH[N(SiMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>7</jats:bold>) and [(Me<jats:sub>3</jats:sub>Si)<jats:sub>2</jats:sub>N]HMeSi–SiMe<jats:sub>3</jats:sub> (<jats:bold>8</jats:bold>). The analogous reaction of <jats:bold>2</jats:bold>, Me<jats:sub>3</jats:sub>SiCl and lithium afforded [(Me<jats:sub>3</jats:sub>Si)<jats:sub>2</jats:sub>N]<jats:sub>2</jats:sub>MeSi–SiMe<jats:sub>3</jats:sub> (<jats:bold>10</jats:bold>) only. [(Me<jats:sub>3</jats:sub>Si)<jats:sub>2</jats:sub>N]MePhSiLi (<jats:bold>11</jats:bold>) and [(Me<jats:sub>3</jats:sub>Si)<jats:sub>2</jats:sub>N]Ph<jats:sub>2</jats:sub>SiLi (<jats:bold>16</jats:bold>) prepared by reaction of <jats:bold>3</jats:bold> and <jats:bold>4</jats:bold> with lithium in THF underwent a partial rearrangement to form the lithium amides [(Li)(Me<jats:sub>3</jats:sub>Si)N]MePhSi–SiMe<jats:sub>3</jats:sub> (<jats:bold>12</jats:bold>) and [(Li)(Me<jats:sub>3</jats:sub>Si)N]Ph<jats:sub>2</jats:sub>Si–SiMe<jats:sub>3</jats:sub> (<jats:bold>17</jats:bold>), respectively, when the temperature raised from –78 °C to room temperature. In the reaction of <jats:bold>5</jats:bold> with lithium in THF at –78 °C, the amide [(Li)(Me<jats:sub>3</jats:sub>Si)N][(Me<jats:sub>3</jats:sub>Si)<jats:sub>2</jats:sub>N]PhSi–SiMe<jats:sub>3</jats:sub> (<jats:bold>21</jats:bold>) was formed. [(Me<jats:sub>3</jats:sub>Si)<jats:sub>2</jats:sub>N]<jats:sub>2</jats:sub>PhSiLi (<jats:bold>20</jats:bold>) was obtained by reaction of <jats:bold>5</jats:bold> with lithium in the Trapp mixture at –110 °C. The silyllithiums <jats:bold>11</jats:bold>, <jats:bold>16</jats:bold>, <jats:bold>20</jats:bold> and the lithium amides <jats:bold>12</jats:bold>, <jats:bold>17</jats:bold>, <jats:bold>21</jats:bold> were trapped with HMe<jats:sub>2</jats:sub>SiCl resulting in the following products: [(Me<jats:sub>3</jats:sub>Si)<jats:sub>2</jats:sub>N]MePhSi–SiMe<jats:sub>2</jats:sub>H (<jats:bold>13</jats:bold>), [(Me<jats:sub>3</jats:sub>Si)<jats:sub>2</jats:sub>N]Ph<jats:sub>2</jats:sub>Si–SiMe<jats:sub>2</jats:sub>H (<jats:bold>18</jats:bold>), [(Me<jats:sub>3</jats:sub>Si)<jats:sub>2</jats:sub>N]<jats:sub>2</jats:sub>PhSi–SiMe<jats:sub>2</jats:sub>H (<jats:bold>24</jats:bold>), [(HMe<jats:sub>2</jats:sub>Si)(Me<jats:sub>3</jats:sub>Si)N]MePhSi–SiMe<jats:sub>3</jats:sub> (<jats:bold>14</jats:bold>), [(HMe<jats:sub>2</jats:sub>Si)(Me<jats:sub>3</jats:sub>Si)N]Ph<jats:sub>2</jats:sub>Si–SiMe<jats:sub>3</jats:sub> (<jats:bold>19</jats:bold>), and [(HMe<jats:sub>2</jats:sub>Si)(Me<jats:sub>3</jats:sub>Si)N][(Me<jats:sub>3</jats:sub>Si)<jats:sub>2</jats:sub>N]PhSi–SiMe<jats:sub>3</jats:sub> (<jats:bold>22</jats:bold>). The silyllithiums <jats:bold>11</jats:bold>, <jats:bold>16</jats:bold>, and <jats:bold>20</jats:bold> were formed directly by reaction of the corresponding aminochlorosilanes with lithium at –78 °C (<jats:bold>11</jats:bold> and <jats:bold>16</jats:bold>) and at –110 °C (<jats:bold>20</jats:bold>), respectively. In the reaction of the aminochlorosilane <jats:bold>6</jats:bold> with lithium in THF at –78 °C a mixture of [(Me<jats:sub>3</jats:sub>Si)<jats:sub>2</jats:sub>N]HPhSiLi (<jats:bold>25</jats:bold>) and [(Me<jats:sub>3</jats:sub>Si)<jats:sub>2</jats:sub>N]HPhSi–SiHPhLi (<jats:bold>26</jats:bold>) was obtained. Compounds <jats:bold>25</jats:bold> and <jats:bold>26</jats:bold> were trapped with HMe<jats:sub>2</jats:sub>SiCl to give [(Me<jats:sub>3</jats:sub>Si)<jats:sub>2</jats:sub>N]HPhSi–SiMe<jats:sub>2</jats:sub>H (<jats:bold>27</jats:bold>) and [(Me<jats:sub>3</jats:sub>Si)<jats:sub>2</jats:sub>N]HPhSi–SiHPh–SiMe<jats:sub>2</jats:sub>H (<jats:bold>28</jats:bold>). The molecular structures of <jats:bold>19</jats:bold>, <jats:bold>22</jats:bold> and <jats:bold>24</jats:bold> were determined.</jats:p>