An ab initio investigation of the electronic structure of ion-pair enolates NH2COCH2TiF3, PH2COCH2TiF3, C6H5COCH2TiF3, C6H5SOCH2TiF3: the influence of the heteroatom. Part II

The electronic structure and the geometry of the trifluorotitanioacetamide, the trifluorotitanioacetylphosphine, the trifluorotitanioacetophenone and the trifluorotitaniomethylphenylsulphoxide have been investigated through a b initio calculations. The different coordination modes, eta(1)-O, eta(3)- and eta(1)-C of the TiF3+ cation have been analysed. The eta(1)-O coordinat ion of the titanium towards the enolate anion is preferred, although in the acetamide enolate anion and the methylphenylsulphoxide enolate anion the e ta(1)-O and the eta(3) coordinations are almost isoenergetic. The eta(1)-C coordination is destabilised in all systems. A comparison between TiF3+ and Li+ shows that TiF3+ is more oxophilic than Li+. (C) 1999 Elsevier Science B.V, All rights reserved.