Reduction of [Cp*Sb]₄ with Subvalent Main-Group Metal Reductants: Syntheses and Structures of [(L¹Mg)₄(Sb₄)] and [(L²Ga)₂(Sb₄)] Containing Edge-Missing Sb₄ Units

详细信息    查看全文

• 作者：Dr. Chelladurai Ganesamoorthy ; Julia Krü ; ger ; Dr. Christoph W&ouml ; lper ; Dr. Anton S. Nizovtsev and Prof. Dr. Stephan Schulz
• 刊名：Chemistry - A European Journal
• 出版年：2017
• 出版时间：February 16, 2017
• 年：2017
• 卷：23
• 期：10
• 页码：2461-2468
• 全文大小：1839K
• ISSN：1521-3765

文摘

[Cp*Sb]₄ (Cp*=C₅Me₅) reacts with [L¹Mg]₂ and L²Ga with formation of [(L¹Mg)₄(μ₄,η^1:2:2:2-Sb₄)] (L¹=iPr₂NC[N(2,6-iPr₂C₆H₃)]₂, 1) and [(L²Ga)₂(μ,η^2:2-Sb₄)] (L²=HC[C(Me)N(2,6-iPr₂C₆H₃)]₂, 2). The cleavage of the Sb−Sb and Sb−C bonds in [Cp*Sb]₄ are the crucial steps in both reactions. The formation of 1 occurred by elimination of the Cp* anion and formation of Cp*MgL¹, while 2 was formed by reductive elimination of Cp*₂ and oxidative addition of L²Ga to the Sb₄ unit. 1 and 2 were characterized by heteronuclear NMR spectroscopy and single-crystal X-ray diffraction, and their bonding situation was studied by quantum chemical calculations.