Titanium(III) trisamidotriazacyclononane: reactions with C60 and radicals |
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Authors: | Barroso Sónia Cui Jinlan Dias Alberto R Duarte M Teresa Ferreira Humberto Henriques Rui T Conceição Oliveira M Ascenso José R Martins Ana M |
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Institution: | Centro de Química Estrutural, Complexo Interdisciplinar, Instituto Superior Técnico, Av. Rovisco Pais 1, 1049-001 Lisboa, Portugal. |
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Abstract: | 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 multistep reaction scheme that involves redox and nucleophilic reactions, presents an imido ligand formed by ligand rearrangement 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 originally neutral triazacyclononane ring. In solution, either 5a or 5b displays additional fluxional processes that consist of its corresponding racemization processes. |
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