Poly[perfluorotitanate(IV)] salts of [H3O]+, Cs+, [Me4N]+, and [Ph4P]+ and about the existence of an isolated [Ti2F9]- anion in the solid state.
The increase in the size of monocations (A(+)) does not favor the formation of [Ti(2)F(9)](-) against [Ti(4)F(18)](2-) salts (with isolated [Ti(2)F(9)](-) or [Ti(4)F(18)](2-) anions, respectively) as previously proposed (Passmore, J.; et al. Angew. Chem., Int. Ed. 2005, 44, 7958-7961). The crystal structure determination of [Me(4)N](+) and [Ph(4)P](+) salts showed that both compounds are [Ti(4)F(18)](2-) salts; i.e., [Me(4)N](2)[Ti(4)F(18)] and [Ph(4)P](2)[Ti(4)F(18)] were obtained instead of [Me(4)N][Ti(2)F(9)] and [Ph(4)P][Ti(2)F(9)]. The product of the reaction of CsF with 2TiF(4) could be formulated as CsTi(2)F(9); however, instead of isolated [Ti(2)F(9)](-) anions, infinite ([Ti(2)F(9)](-))(n) double chains are present. In the case of H(3)OTi(2)F(9), a similar result was obtained. On the basis of the similarities of vibrational spectra of CsTi(2)F(9) and NF(4)Ti(2)F(9), it is also unlikely that the latter consists of isolated [Ti(2)F(9)](-) ions.
Mazej
Zoran
Z
Department of Inorganic Chemistry and Technology, Jozef Stefan Institute, Jamova 39, SI-1000 Ljubljana, Slovenia. zoran.mazej@ijs.si
Goreshnik
Evgeny
E