Titanium Triamidotriamine Compounds: Syntheses, Structures and Redox Properties

✍ Scribed by Ana M. Martins; José R. Ascenso; Cristina G. de Azevedo; Alberto R. Dias; M. Teresa Duarte; Humberto Ferreira; M. João Ferreira; Rui T. Henriques; M. Amélia Lemos; Li Li; João F. da Silva

• Publisher: John Wiley and Sons
• Year: 2005
• Tongue: English
• Weight: 173 KB
• Volume: 2005
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200400813

✦ Synopsis

Abstract

The preparation of 1,4,7‐{NH(2‐C~6~H~4~F)SiMe~2~}~3~‐1,4,7‐triazacyclononane (H~3~N~3‐F~[9]N~3~) and 1,4,8‐{N(H)PhSiMe~2~}~3~‐1,4,8‐triazacycloundecane (H~3~N~3~[11]N~3~), and their sodium derivatives Na~3~N~3‐F~[9]N~3~(THF)~2~ and Na~3~N~3~[11]N~3~(THF)~2~, is described. The reaction of [TiCl~3~(THF)~3~] with Na~3~N~3‐F~[9]‐N~3~(THF)~2~ and Na~3~N~3~[11]N~3~(THF)~2~ leads to [Ti{N~3‐F~[9]N~3~}] and [Ti{N~3~[11]N~3~}]. The titanium complexes react readily with I~2~ to give the Ti^IV^ derivatives [Ti{N~3‐F~[9]N~3~}]I and [Ti{N~3~[11]N~3~}]I. All titanium compounds display distorted trigonal prismatic geometries where the metal is coordinated to the six nitrogen donors. Fluxional processes that convert the conformations of the five‐ and six‐membered metallacycles and the Δ and Λ enantiomers of [Ti{N~3~[11]N~3~}]I have been identified in solution. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)