Oxidation lanthanide-assisted

We now turn to the 3d series elements. The dihalides and trihalides can be treated as ionic solids, although the chlorides, bromides and iodides adopt layer structures which might be better viewed as polymeric covalent crystals. In Fig. 5.2 the third ionisation energies of the 3d atoms are plotted alongside those of the lanthanides. These all involve the removal of an electron from a 3d orbital from Fe onwards, the orbital concerned is doubly occupied so that spin-pairing energy assists the ionisation. This accounts for the break between Mn and Fe, as previously discussed (Section 4.3). The increase from Sc to Mn, and from Fe to Zn, is much sharper than the corresponding increases in the lanthanide series. However, the break at the half-filled shell is less abrupt for the 3d series. This explains why the II oxidation state - which is... 

For the first time, catalytic activity of lanthanide isopropoxides was detected in the TBHP (tert-butylhydroperoxide) assisted oxidation of allylic alcohols to epoxyalcohols (Eq. 26) [231], For example epoxy geraniol was obtained in up to 96% yield by using YbfOiPr in the presence of molecular sieves (4 A) [232]. 

Han et al. (2008) reported the s)mthesis of heavy lanthanide sesqui-oxide (R2O3, R = Y, Dy, Ho, Er) nanobelts by thermolysis of solid rare earth nitrate hydrates in a dodecylamine/l-octadecene mixed solvent system. The nitrate hydrates showed poor solubility in the mixed solvent, and the heat-transport differences between the liquid and the solid assisted in separation of the nucleation and growth processes. 

Sol-gel processes are also suitable for lanthanide oxide formation, as could be shown by the use of Tb(acac)3 and Dy(OBu- )3 in acetylacetone" . Tb203 crack- and pine-hole-free, dense and smooth microstructured buffer layers were produced on nickel tapes by a reel-to-reel continuous sol-gel process. The authors report that the film properties can be strongly influenced by solution components, temperature, time and atmosphere. Nanocrystalline mesoporous dysprosium oxide Dy203 with narrow monomodal pore size distribution can be approached by a combined sol-gel process with a surfactant-assisted templating technique . The spherical Dy203 nanoparticles were formed with aggregations. 

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