Ligand exchange dynamics in molecular titanium tetrafluoride complexes cis-TiF4L2

The tetrafluoro complexes TiF4L2 (L = TPPO, DMSO, TMP, Et2O, MeCN) were syn thesized, and ligand exchange dynamics in them were studied. Ligand exchang e in cis-TiF4(TMP)(2) was found to follow the dissociative mechanism; side ligand exchange processes that occur at elevated temperatures were disclose d by 2D NOESY. A full F-19 NMR line-shape analysis gave the following excha nge activation parameters: DeltaH(not equal) = 71.55(8) U/mol, DeltaS(not e qual) = 70(3) J/(mol K), DeltaG(254.7)(not equal) = 53.7(2) U/mol, and Delt aG(213)(not equal) = 56.6(2) U/mol. The DeltaG(T)(not equal) values for cis -TiF4L2 were determined, and qualitative correlation between the thermodyna mic and kinetic stabilities of titanium tetrafluoride complexes was establi shed.