A. Demsar et al., Calcium fluoride incorporated in soluble organometallics: adduct formationand solution dynamics, J CHEM S DA, (23), 1998, pp. 4043-4047
Citations number
16
Categorie Soggetti
Inorganic & Nuclear Chemistry
Journal title
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
The recrystallization of [{Ti(C5Me5)F-3}(4)CaF2] 1 and [{Ti(C5Me4Et)F-3}(4)
CaF2] 2 in the presence of an excess of hmpa (hexamethylphosphoramide) resu
lted in the formation of [{Ti(C5Me5)F-3}(4)(CaF2)(hmpa)] 3 and [{Ti(C5Me4Et
)F-3}(4)(CaF2)(hmpa)] 4, respectively. The adducts 3 and 4 were spectroscop
ically characterized and the molecular structure of 4 was determined, showi
ng a co-ordination of calcium by eight fluorine atoms from two [Ti-2(C5Me4E
t)(2)F-7](-) moieties and by an oxygen atom of an hmpa ligand. Adduct forma
tion and solution behavior of 2 in different solvents was studied by H-1 an
d F-19 NMR and variable-temperature NMR. A temperature dependent equilibriu
m between 2 and a solvated form 2.solv (solv = solvent molecule) is propose
d. With increase of the temperature the equilibrium between 2 and 2.solv wa
s observed to be entropy-shifted to the non-solvated form.