An ab initio investigation of the electronic structure of ion-pair enolates NH_2COCH_2TiF_3, PH_2COCH_2Tif_3, C_6H_5COCH_2TiF_3, C_6H_5SOCH_2TiF_3: the influence of the heteroatom. Part II

摘要

The electronic structure and the geometry of the trifluorotitanioacetamide, the trifluorotitanioacetylphosphine, the trifluorotitanioacetophenone and the trifluorotitaniomethylphenylsulphoxide have been investigated through ab initio calculations. The different coordination modes, #eta#~1-O, #eta#~3 - and #eta#~1-C of the TiF_3~+ cation have been analysed. The #eta#~1-O coordination of the titanium towards the enolate anion is preferred, although in the acetamide enolate anion and the methylphenylsulphoxide enolate anion the #eta#~1-O and the #eta#~3 coordinations are almost isoenergetic. The #eta#~1-C coordination is destabilised in all systems. A comparison between TiF_3~+ and Li~+ shows that TiF_3~+ is more oxophilic than Li~+.