Titanium(III) Trisamidotriazacyclononane: Reactions with C60 and Radicals

详细信息    查看全文

• 作者：Só ; nia Barroso ; Jinlan Cui ; Alberto R. Dias ; M. Teresa Duarte ; Humberto Ferreira ; Rui T. Henriques ; M. Concei&ccedil ; ã ; o Oliveira ; José ; R. Ascenso ; and Ana M. Martins
• 刊名：Inorganic Chemistry
• 出版年：2006
• 出版时间：May 1, 2006
• 年：2006
• 卷：45
• 期：9
• 页码：3532 - 3537
• 全文大小：135K
• 年卷期：v.45,no.9(May 1, 2006)
• ISSN：1520-510X

文摘

The reaction of titanium trisamidotriazacyclononane, [Ti{N(Ph)SiMe₂}₃tacn] (1), with C₆₀ led to the synthesis of[Ti{N(Ph)SiMe₂}₃tacn]C₆₀ (2) in high yield. Treatment of 2 with PhCH₂Br led to the formation of [Ti{N(Ph)SiMe₂}₃tacn]Br and the radical PhCH₂C₆₀ (3). The reaction of CH₃I with 1 gives two products. One is [Ti{N(Ph)SiMe₂}₃tacn]I (4), which results from the oxidation of 1 by an I radical. The other product, 5, resulting from a multistepreaction scheme that involves redox and nucleophilic reactions, presents an imido ligand formed by ligandrearrangement upon C-N bond cleavage. In solution, an exchange process that corresponds to a reversible 1,3-silyl shift between two Ti-bonded N atoms leads to isomers 5a and 5b. This equilibrium transforms an imido(TiNPh) into an amido ligand (Ti{NPh}SiMe₂CH₂Ph) with concomitant generation of an anionic moiety in the originallyneutral triazacyclononane ring. In solution, either 5a or 5b displays additional fluxional processes that consist of itscorresponding racemization processes.