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

Abstract

We report the synthesis and structural characterisation of two titanium(IV) complexes. A new titanium(IV) complex bearing four picolinato ligands, denoted as Ti(pic) 4 , has been prepared under solvothermal conditions. This complex identified by single-crystal diffraction is a new example of an octacoordinated environment for titanium(IV) and is close to an ideal triangular dodecahedron. A second synthesis of a [a]

Titanium‐Oxo Clusters with Bi‐ and Tridentate Organic Ligands: Gradual Evolution of the Structures from Small to Big

“… R=Et: R’=C 6 H 4 OPh [84] R= i Pr: R’=H, [29] Me, [85,86] Et, [87] Bu, [31] i Bu, [88] t Bu, [89] CHCl 2 , [24] cyclohex‐3‐enyl, [64] CH 2 Ph, [90] CH 2 ‐naphthyl, naphthyl, [91] C 6 H 4 Ph, C 6 H 4 t Bu, [92] anthracenyl, [62] adamantyl, [54] C 6 H 4 COO i Pr, [14b] C 6 H 4 NH 2 , [93] C 6 H 3 (X)NHMe (X=H, F, Cl), [93b] C 6 H 4 NMe 2 , [54] C 5 H 4 N, [25] C 5 H 3 N−CO 2 i Pr, [94] ferrocenyl [88,91] R=Bu: R’= t Bu [95] R= i Bu: R’= t Bu, [95] CMe 2 Et [83] R= t Bu: R’=Et, [31] CMe 2 Et, CH 2 t Bu [44] R=CH 2 t Bu: R’= i Pr, [14a] Ph [73] R=SiMe 3 : R’= t Bu, [95] CH 2 t Bu, CMe 2 Et [95a] …”

“…R= i Pr: R’=H, [29] Me, [85,86] Et, [87] Bu, [31] i Bu, [88] t Bu, [89] CHCl 2 , [24] cyclohex‐3‐enyl, [64] CH 2 Ph, [90] CH 2 ‐naphthyl, naphthyl, [91] C 6 H 4 Ph, C 6 H 4 t Bu, [92] anthracenyl, [62] adamantyl, [54] C 6 H 4 COO i Pr, [14b] C 6 H 4 NH 2 , [93] C 6 H 3 (X)NHMe (X=H, F, Cl), [93b] C 6 H 4 NMe 2 , [54] C 5 H 4 N, [25] C 5 H 3 N−CO 2 i Pr, [94] ferrocenyl [88,91] …”

“…Ti 6 O 6 (O i Pr) 6 (O 2 C−C 6 H 4 −CO 2 i Pr) 6 was obtained from a mixture of Ti(O i Pr) 4 , phthalic anhydride and acetic acid [14b] and Ti 6 O 6 (O i Pr) 6 (O 2 C−C 5 H 3 N−CO 2 i Pr) 6 from pyridine‐3,4‐dicarboxylic anhydride. [94] When Ti(O i Pr) 4 is reacted with phthalic anhydride alone, the anhydride can substitute OR groups, resulting in the compound Ti 2 (O i Pr) 6 (O 2 C−C 6 H 4 −CO 2 i Pr) 2 ( i PrOH), but there is no source for oxo groups. However, when acetic acid is added, water is produced through formation of iso ‐propyl acetate, and a cluster is obtained.…”

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

“…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.…”

Structural Characterization and Bioactivity of a Titanium(IV)-Oxo Complex Stabilized by Mandelate Ligands

“…These compounds have found applications in diverse technologies, including hydrogen production or water purification [3,4]. Previous research led to the synthesis of TOCs with cores containing from 2 to 44 titanium atoms [5][6][7][8][9][10][11][12], with the largest group consisting of compounds with four-and six-nuclear cores [13][14][15][16][17]. The cores {Ti a O b } of TOCs can be stabilized by alkoxide groups, as well as carboxylate or phosphonate ligands, although β-diketonate, β-ketoester, and sulfonate ligands have also been employed [5,18,19].…”