Low-Coordinate Bismuth Cations

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• 作者：Ryan J. Schwamm ; Benjamin M. Day ; Martyn P. Coles ; Christopher M. Fitchett
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：April 7, 2014
• 年：2014
• 卷：53
• 期：7
• 页码：3778-3787
• 全文大小：474K
• 年卷期：v.53,no.7(April 7, 2014)
• ISSN：1520-510X

文摘

Chloride abstraction from the diamido-bismuth compound Bi(Me₂Si{NAr}₂)Cl (1, Ar = 2,6-i-Pr₂C₆H₃) using MCl₃ (M = Al, Ga) is a facile route to cationic species. Stoichiometric reactions afford the tetrachlorometallate salts [Bi(Me₂Si{NAr}₂)][MCl₄] (2a, M = Al; 3a, M = Ga), whereas reaction with 0.5 equiv of the group 13 reagent gives the 渭-chlorido bridged cations [{Bi(Me₂Si{NAr}₂)}₂(渭-Cl)][MCl₄] (2b, M = Al; 3b, M = Ga). The crystal structure of 2a shows a formally two-coordinate bismuth cation, with a Bi路路路Cl contact to the [AlCl₄]^{鈭?/sup> anion, whereas the structure of 3b shows a total of three Bi路路路Cl contacts to [GaCl₄]鈭?/sup>. Both species associate as {1:1}₂ dimers in the solid state through additional Bi路路路Cl interactions. Attempted preparation of cationic complexes using either NaBR₄ (R = Ph, Et) or [HNEt₃][BPh₄] were unsuccessful. Instead of forming the borate salts, the neutral compounds Bi(Me₂Si{NAr}₂)R (4, R = Et; 5, R = Ph) were isolated as a result of aryl/alkyl transfer from boron to bismuth.}