In toluene as medium, the tetra(cyclopentadienyl) derivatives of Group 4 elements, MCp4 (MTi, Zr, Hf), have been prepared in high yields from MCp2Cl2 and NaCp. The reactivity of ZrCp4 with species containing active protons such as Ph3SiOH or strong acids has been studied. Substituted bis(cyclopentadienyl) derivatives were produced except in the case of the reaction between ZrCp4 and CF3SO3H. In this case, the tris(cyclopentadienyl) derivative ZrCp3(CF3SO3) was obtained as a pale yellow crystalline material, reactive with water to give the m-oxo derivative of zirconium(IV), [ZrCp2(CF3SO3)]2O, which has been characterized by standard methods and by X-ray diffraction. Crystal data: C22H20F6O7S2Zr2, M756.96 g mol1, monoclinic, space group C2:c (no. 15), a19.525(4), b9.028(2), c16.152(5) A° , b107.31(2)°, V2718.2(1) A° 3, Z4, dcalc1.850 g cm3, l(Cu–Ka) 1.54184 A° , T291 K, m85.66 cm1, F(000)1496, R0.054, Rw0.049.
The tetracyclopentadienyls of titanium, zirconium and hafnium: new synthetic procedures and reactivity
CALDERAZZO, FAUSTO;PAMPALONI, GUIDO;
1998-01-01
Abstract
In toluene as medium, the tetra(cyclopentadienyl) derivatives of Group 4 elements, MCp4 (MTi, Zr, Hf), have been prepared in high yields from MCp2Cl2 and NaCp. The reactivity of ZrCp4 with species containing active protons such as Ph3SiOH or strong acids has been studied. Substituted bis(cyclopentadienyl) derivatives were produced except in the case of the reaction between ZrCp4 and CF3SO3H. In this case, the tris(cyclopentadienyl) derivative ZrCp3(CF3SO3) was obtained as a pale yellow crystalline material, reactive with water to give the m-oxo derivative of zirconium(IV), [ZrCp2(CF3SO3)]2O, which has been characterized by standard methods and by X-ray diffraction. Crystal data: C22H20F6O7S2Zr2, M756.96 g mol1, monoclinic, space group C2:c (no. 15), a19.525(4), b9.028(2), c16.152(5) A° , b107.31(2)°, V2718.2(1) A° 3, Z4, dcalc1.850 g cm3, l(Cu–Ka) 1.54184 A° , T291 K, m85.66 cm1, F(000)1496, R0.054, Rw0.049.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
