The conversion of multinuclear μ-oxo titanium(iv) species in the reaction of Ti(OiBu)4 with branched organic acids; results of structural and spectroscopic studies

Abstract

Crystalline materials have been synthesized in reactions of titanium(iv) tetraisobutoxide with branched organic acids (HOOCR', R' = CMe(2)Et, (t)Bu, CH(2)(t)Bu) in the molar ratio 1:1 at room temperature under Ar atmosphere. Particular attention has been paid to the structural and spectral characterization of metastable intermediate complexes of general formula [Ti(7)O(9)(O(i)Bu)(4)(HO(i)Bu)(OOCCMe(2)Et)(6)](2) (1) and [Ti(6)O(5)(O(i)Bu)(6)(OOC(t)Bu)(8)] (3), and their conversion towards more structurally stable compounds [Ti(6)O(6)(O(i)Bu)(6)(OOCC(Me)(2)Et)(6)] (2) and [Ti(6)O(6)(H(2)O)(2)(O(i)Bu)(6)(OOC(t)Bu)(6)] (4). The hexanuclear structure of (5) ([Ti(6)O(6)(O(i)Bu)(6)(OOCCH(2)(t)Bu)(6)]) has been postulated on the basis of IR and (13)C NMR spectroscopic data analysis. The possible reaction pathways which may occur during the formation of the above mentioned compounds are also discussed.

Synthesis, structural and physicochemical characterization of a new type Ti6-oxo cluster protected by a cyclic imide dioxime ligand

“…32 In the interior of the {Ti6O5} cluster there is a void space with dimensions 4.11 × 4.52 Å. To the best of our knowledge, though the {Ti6O5} core has been reported only once, 37 its topology in compound 1( Fig. 2A) is quite different in comparison with the previously reported one (Fig.…”

“…3a), 36,37 and the second one consisting of two planar {Ti3O3} units parallel to each other (Fig. 3b); 12,[27][28][29][30][31][32][33][34][35][36][37][38][39]42 (ii) six configurations with the six Ti IV lying almost on a planar arrangement {Ti6 55 and {Ti6(μ2-O)9} ( Fig. 3f), 56 exhibiting two {Ti3(μ2-O)3} units parallel to each other; and (iv) {Ti6(μ3-O)2(μ2-O)2} ( Fig.…”

Tetranuclear Oxo-Titanium Clusters with Different Carboxylate Aromatic Ligands: Optical Properties, DFT Calculations, and Photoactivity

“…The possible interactions between inorganic and organic components may result in an improvement of structural properties of the polymer as well as its thermal, mechanical, and barrier properties due to cross-linking and filling. The unique properties of oxo-clusters, e.g., photochromicity, catalytic/biological or magnetic activity, can give entirely new properties to the composite material compared to the base polymer [ 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 ]. Therefore, studies on TOC synthesis of the titanium oxide core with the desirable architecture, size, and physicochemical properties are important for the production of novel inorganic–organic composite materials [ 17 ].…”

Structural Investigation of Pyridinecarboxylato Titanium(IV) Complexes: An Uncommon Monomeric Octacoordinated Complex vs. a Hexaprismatic Architecture

“…The IR spectrum of the crystalline solid shows a single band at ν = 1726 cm -1 related to the C=O stretch in the ester group (Supporting Information). [10,20,[42][43][44][45][46][47][48][49][50][51][52] The structure also highlights the formation of an ester group para oriented on the pyridine ring of the carboxylato ligand. The complex [Ti 6 (μ 3 -O) 6 (OiPr) 6 (μ-O 2 CC 5 H 3 NCOOiPr) 6 ] crystallises in the P1 space group with one molecule per unit cell.…”