Iron(iii) and titanium(iv) oxoalkoxide chemistry: synthetic, structural, magnetochemical and spectroscopic studies of [Ti₃(μ₃-OPrⁱ)₂(μ-OPrⁱ)₃(OPrⁱ)₆][FeCl₄] and [Fe₅(μ₅-O)(μ-OPrⁱ)₈Cl₅]

ɛ‐caprolactone and lactide polymerization promoted by an ionic titanium(IV)/iron(III) polynuclear halo‐alkoxide

“…This reveals that polymers produced with monomer/ A proportions up to 750 generate EPR spectra typical of high spin iron(III) centers ( S = 5/2) in rhombic ( g = 4.3) and axial ( g = 2.0) environments . The spectrum in Figure is similar to the one recorded earlier by our research group for alcoholic solutions of A and could come from aggregates of [FeCl 4 ] − anions formed during the precipitation of the polymers with methanol. Conversely, samples obtained with the smallest amount of A (1000:1 molar proportion of monomer to A ) presented only residual iron(III) signals.…”

“…[Ti(OPr i ) 4 ] (97%) was obtained from Aldrich and distilled under N 2 prior to use. Complexes [Ti 3 (µ 3 ‐OPr i ) 2 (µ‐OPr i ) 3 (OPr i ) 6 ][FeCl 4 ] ( A ) and [N(CH 3 ) 4 ][FeCl 4 ] were prepared according to previous literature reports. rac ‐Lactide ( rac ‐LA, 99%) and L ‐ lactide (L‐LA, 98%) were obtained from Alfa Aesar and dried under vacuum in the presence of phosphorus pentoxide.…”

“…In this work, the title compound, [Ti 3 (µ 3 ‐OPr i ) 2 (µ‐OPr i ) 3 (OPr i ) 6 ][FeCl 4 ] (complex A , Supporting Information Fig. S1) has been used as initiator in the polymerization of ɛ‐caprolactone and rac‐ and L‐lactides. It contains a trinuclear titanium(IV) cation that can be seen as a modification of the known Ti 3 (O)(OR) 10 archetype in which the bridging oxo (O 2− ) ligand has been replaced by one isopropoxide.…”

“…It contains a trinuclear titanium(IV) cation that can be seen as a modification of the known Ti 3 (O)(OR) 10 archetype in which the bridging oxo (O 2− ) ligand has been replaced by one isopropoxide. The neutral Ti 3 (O)(OR) 10 unity is relatively common in titanium(IV) chemistry, differently from its cationic counterpart [Ti 3 (OR) 11 ] + in A , whose occurrence has only been reported in four occasions …”

Oxoethoxide Chlorides – Representatives of Oligonuclear Alkoxide Complexes of Gallium: Penta‐ and Dodecanuclear Molecules

“…Four shorter bridges are placed between the apical hexacoordinate metal atom and the equatorial metal atoms (designated as (5)(6) in Table 1), and the other four longer bridges bind the trigonal bipyramidal coordinated Ga atoms together in the equatorial plane (designated as in Table 1), see Figure 1. The bonding parameters for 1 are practically identical to those of its structural analogsderivatives of aluminium and iron(III), [15][16][17][18][19] see Table 1. The only (minor) difference between the compounds presented in Table 1 12 Cl.…”