Synthesis, characterization and soft transformation of some bis(cyclopentadienyl) Ti(IV) and Zr(IV) complexes of Schiff's base ligands to nano‐sized titania or zirconia materials

Synthesis and characterization of some bis(cyclopentadienyl)titanium(IV) complexes with internally functionalized oximes(LH): sol–gel transformations of Cp2TiCl2, Cp2TiClL and Cp2TiL2 to nano‐sized anatase titania

“…[5b,c,7,9 -11] The absence of hydroxyl group absorption of the ligand in the region around ∼3300 cm −1 in all these derivatives suggests the deprotonation of the OH group and formation of the Ti-O bond which is further supported by the appearance of strong intensity bands in the region 515-546 cm −1 assigned to υ(Ti-O) bond. [7] The υ(C N) and υ(N-O) vibrations are shifted towards lower wave number (∼25 cm −1 ) as compared with the free oximes, indicating the side-on coordination mode of oximato moieties in the solid state. [9] The side-on coordination mode of oximato moiety in the solid state further gets support by the appearance of a strong intensity band in the region 476-494 cm −1 assignable to υ(Ti-N) vibrations.…”

“…[9] The side-on coordination mode of oximato moiety in the solid state further gets support by the appearance of a strong intensity band in the region 476-494 cm −1 assignable to υ(Ti-N) vibrations. [7] Absorptions due to Cp rings are observed around 2950, 1440, 1025 and 840 cm −1 , which may be assigned to υ(C-H) (stretching), υ(C-C), υ(C-H) (out-of-plane bending) and υ(C-H) (in-plane bending) modes, respectively, suggesting that the Cp groups are attached to the metal via η 5 bonding mode in all the complexes. [5b,c] …”

“…[6] Some Schiff's base complexes of titanocene/zirconocene yield predominantly nano-sized anatase titania/tetragonal zirconia materials by sol-gel technique. [7] Oximes including functionalized oximes are excellent chemical modifiers and surfactants for the synthesis of anatase titania. [8] They exhibit a tendency to change their coordination mode from side-on [9] to end-on [10] to bridging [11] as revealed by the single crystal X-ray diffraction studies of a considerable number of metal complexes (Fig.…”

Synthesis and Characterisation of Modified Germanium (IV) Isopropoxide with Internally Functionalised oximes: Soft Transformation of Some of These to Pure Nano-Sized Germania

“…12 The alkoxy and glyoxy derivatives of tetravalent germanium have received less attention as compared to other tetravalent elements (Si, Sn, Ti and Zr). [13][14][15] Alkoxy derivatives of Ge(IV) generally prefer a tetracoordinated structure even with alkoxy alkanols. 16 Penta-and hexacoordinated-derivatives of Ge(IV) with complex organic moieties have also been cited in the literature.…”