A General and Facile One-Step Synthesis of Imido-Titanium(IV) Complexes: Application to the Synthesis of Compounds Containing Functionalized or Chiral Imido Ligands and Bimetallic Diimido Architectures

• Published in: European Journal of Inorganic Chemistry 2006-11, Vol.2006 (22), p.4503-4518
• Main Authors: Lorber, Christian, Choukroun, Robert, Vendier, Laure
• Format: Article
• Language: English
• Subjects: Imido; Multiple bonds; N ligands; Synthesis design; Titanium
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.200600475

One‐pot reactions of Ti(NMe2)4 with a wide range of primary alkyl, aryl, and silylamines RNH2 in the presence of excess chlorotrimethylsilane produced the corresponding imido–titanium(IV) complexes [Ti(=NR)Cl2(NHMe2)2] (1a–j), in which R = tBu, 1‐adamantane, Ph3C, Ph3Si, Ph, 2,6‐iPr2–C6H3, 2,6‐Cl2–C6H3, 2,6‐Br2–4‐Me–C6H2, C6F5, and 3,5‐(F3C)2–C6H3. This general synthesis, which starts from commercially available reagents, represents a simple and direct route to imido complexes. Reaction of complexes 1 with pyridine afforded the six‐coordinate tris‐pyridine adducts [Ti(=NR)Cl2(Py)3] (2). Another advantage of this method is its tolerance to other functional groups; complexes that contain halides, ether, dialkylamino, cyano, ethynyl, olefin, and nitro substituents on the imido moiety have been prepared. The use of enantiomerically pure primary amines affords the first group of titanium complexes that contain chiral imido groups, and the use of diamines produces diimido complexes. Alternatively, CH3I has been used as an alkylating agent to generate titanium–imido complexes of the type [Ti(NR)I2(THF)2]2. All compounds were fully characterized by spectroscopic methods (IR, 1H NMR, 13C NMR) and elemental analysis. Some of the compounds were also analyzed by single‐crystal X‐ray diffraction studies. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)