Titanium(III) trisamidotriazacyclononane: reactions with C60 and radicals

Inorganic Chemistry
Sónia BarrosoAna M Martins

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.

References

Jan 1, 1995·Acta Crystallographica. Section A, Foundations of Crystallography·R H Blessing
Feb 12, 2000·Angewandte Chemie·R Kempe
Dec 26, 2001·Chemical Reviews·C A Reed, R D Bolskar
Apr 19, 2002·Journal of the American Chemical Society·Parimal PaulChristopher A Reed
Jun 24, 2003·Inorganic Chemistry·Bernardo MonteiroNoémia Marques
May 22, 2004·Chemical Communications : Chem Comm·Christian G Claessens, Tomás Torres
Apr 20, 2005·Accounts of Chemical Research·Peter D W Boyd, Christopher A Reed
Nov 22, 2005·Inorganic Chemistry·Ana M MartinsJosé A B Ferreira

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Citations

Dec 14, 2011·Inorganic Chemistry·Luis G Alves, Ana M Martins
Nov 28, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Luis G AlvesAna M Martins
Oct 2, 2007·Chemistry : a European Journal·Alison R FoutDaniel J Mindiola
Mar 9, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Hong-Bo TongDian-Sheng Liu
Jan 30, 2007·Inorganic Chemistry·Humberto FerreiraAna M Martins
Dec 4, 2008·Inorganic Chemistry·Marco W Bouwkamp, Auke Meetsma

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