Single-Source Precursors of Lead Titanate: Synthesis, Molecular Structure and Reactivity of Pb2Ti2(.mu.4-O)(.mu.3-O-i-Pr)2(.mu.-O-i-Pr)4(O-i-Pr)4

Abstract

The reaction between Ti(0-i-Pr)4 and [Pb(0-i-Pr)2]= or Pb40(0-z-Pr)6 offers the mixed-metal oxoalkoxide Pb2-Ti2(M4-0)(M3-0-i-Pr)2(M-0-i-Pr)4(0-z-Pr)4 (1) which has been characterized by crystallography at -120 °C. 1 belongs to the monoclinic space group P2\ln with a = 10.286( 14) k,b = 22.564(4) Á, c = 18.709(5) Á, ß = 97.93(5), V = 4301(6) Á* 123, and Z = 4. Compound 1 represents the first example of a structurally characterized "single-source" precursor having a Pb:Ti stoichiometry appropriated for PbTiOg. The 1:1 stoichiometry between the metals is retained by reaction between 1 and acetic acid or acetylacetone (1:2 molar ratio), Pb2Ti20(0Ac)2(0i-Pr)g (2) and Pb2TÍ20(acac)2(0-z-Pr)8 (3) being obtained respectively. All compounds have been isolated in high yields and were characterized by microanalysis, FT-IR and NMR ( , 13C, and 207Pb). Hydrolysiscondensation reactions of the various species giving lead titanate have been achieved.

A structural study of amorphous alkoxide-derived lead titanium complexes

“…6), the near-edge structure shows yet another, significantly different shape. The measured Pb-Ti distance of 3.37Å is, however, higher than the Pb-Ti distance 3.23Å as reported by Daniele et al 29 The fivefold coordination of Ti atoms is also con- however, a homogeneous model of a single trimeric structure fits all the measured parameters. Similar shapes of pre-edge peaks were observed in Ti-Si mixed amorphous oxides where Ti atoms were shown to be 5-coordinated; however, a possibility of a mixture of fourfold and sixfold coordination was not excluded.…”

“…3). [12][13][14]29 No conclusions can be drawn upon relative quantities of the acetate groups in the two gels. [12][13][14]29 No conclusions can be drawn upon relative quantities of the acetate groups in the two gels.…”

A General Soft‐Chemistry Route to Perovskites and Related Materials: Synthesis of BaTiO3, BaZrO3, and LiNbO3 Nanoparticles

“…[20] An oxo bridge could be formed by the reaction of two alkoxide groups bonded to two different metal centers by elimination of an organic ether. This ether-elimination route was postulated in the formation of a mixed-metal oxo alkoxide obtained from the reaction between titanium isopropoxide and lead isopropoxide, [21] but was never further developed. However, preliminary results show that other elimination reactions may also be involved in the formation of these compounds, and further investigations are under way.…”

A General Soft‐Chemistry Route to Perovskites and Related Materials: Synthesis of BaTiO3, BaZrO3, and LiNbO3 Nanoparticles

“…An oxo bridge could be formed by the reaction of two alkoxide groups bonded to two different metal centers by elimination of an organic ether. This ether‐elimination route was postulated in the formation of a mixed‐metal oxo alkoxide obtained from the reaction between titanium isopropoxide and lead isopropoxide,21 but was never further developed. However, preliminary results show that other elimination reactions may also be involved in the formation of these compounds, and further investigations are under way.…”