Synthesis, characterization and properties of titanium phosphonate clusters

Hayami, Ryohei; Sagawa, Tadashi; Tsukada, Shinya; Yamamoto, Kazuki; Gunji, Takahiro

doi:10.1016/j.poly.2018.02.030

Cited by 14 publications

(12 citation statements)

References 49 publications

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“… R′′=Me, t Bu: L=DMSO [126] R′′=Ph: L=THF,[ 127 , 128 ] DMSO, [45] imidazole [129] R′′=naphthyl: L=THF [128] R′′=xylyl: L= i PrOH [120] R′′=4‐C 6 H 4 X (X=OMe, F, Cl, Br): L= i PrOH. [128] …”

Section: Phosphonato‐substituted Titanium Oxo Clustersmentioning

confidence: 99%

“…However, one of the μ 3 ‐O 3 PR′′ ligands of the parent 3+1 compound is replaced by a PO 4 group which additionally connects the single Ti atoms with each other. [131] Ti 7 O 2 (O i Pr) 12 (R′′PO 3 ) 6 (R=CH 2 CH 2 CH 2 Cl, CH 2 Ph, [120] CH 2 C 6 H 4 Br, C 6 H 4 Br [128] ) has a 3+1+3 (“sandwich”) structure, where a second Ti 3 unit is coordinated to the single [TiO 6 ] octahedron. To this end, the neutral ligand L and both terminal OR groups in the 3+1 structure are replaced by the oxygen atoms of three 3.111 R′′PO 3 ligands (that is, the central titanium atom is coordinated by six oxygen atoms of six R′′PO 3 ligands).…”

Section: Phosphonato‐substituted Titanium Oxo Clustersmentioning

confidence: 99%

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

Schubert

2021

Chemistry A European J

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Homometallic titanium oxo clusters are one of the most important groups of metal oxo clusters, with more than 300 examples characterized by X‐ray structure analyses. Most of them are uncharged and are obtained by partial hydrolysis and condensation of titanium alkoxo derivatives. The cluster cores, ranging from 3 to >50 titanium atoms, are stabilized by organic ligands. Apart from residual OR groups, carboxylato and phosphonato ligands are most frequent. The article critically reviews and categorizes the known structures and works out basic construction principles by comparing the different cluster types.

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Section: Phosphonato‐substituted Titanium Oxo Clustersmentioning

confidence: 99%

Section: Phosphonato‐substituted Titanium Oxo Clustersmentioning

confidence: 99%

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

Schubert

2021

Chemistry A European J

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“…An analogous structure having phenylphosphonic acid ligands instead of tert-butylphosphonic acid was recently reported. 44 In the Ti(acac) 2 i OPr 2 precursor there are two acac and two i OPr ligands per titanium but in compound 6 there are only one of each ligand per titanium. The acac-ligand is chelating and generally considered to be strongly bound to Ti(IV) centers.…”

Section: Molecular Structuresmentioning

confidence: 99%

Titanium phosphonate oxo-alkoxide “clusters”: solution stability and facile hydrolytic transformation into nano titania

et al. 2020

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“…An insoluble solid was immediately formed after the hydrolysis of Ti 4 P 3 Ph in THF. Ti 4 P 3 Ph showed high stability at a concentration lower than 10 wt% in THF [ 16 ] ; therefore, the stability was dependent on the concentration. Ti 4 P 3 Ph in toluene underwent an equilibrium reaction with [Ti 4 P 3 Ph] 2 .…”

Section: Resultsmentioning

confidence: 99%

“…We previously reported the molecular stability of [Ti 4 (μ 3 ‐O)(O i Pr) 5 (μ‐O i Pr) 3 (O 3 PPh) 3 ]·thf (Ti 4 P 3 Ph) in tetrahydrofuran (THF) or toluene in the absence of water by nuclear magnetic resonance (NMR) spectroscopy. [ 16 ] Metal alkoxide in acetone is known to form hydroxy group via nonhydrolysis reaction. [ 25,26 ] Thus, a hydrolysis–polycondensation of Ti 4 P 3 Ph behaves differently depending on solvents and may affect the structure and properties of gel.…”

Section: Introductionmentioning

confidence: 99%

Sol–gel reaction of titanium phosphonate alkoxide cluster

Tsukagoshi

Sato

Yamamoto

et al. 2022

Applied Organom Chemis

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The synthesis and properties of titanium phosphonate cluster molecules have been investigated; however, nothing has been done to study not only the catalytic ability of a hydrolyzed cluster but also a behavior of hydrolysis–polycondensation by solvents. The sol–gel reaction of [Ti4(μ3‐O)(OiPr)5(μ‐OiPr)3(O3PPh)3]·thf (Ti4P3Ph) was performed in tetrahydrofuran (THF), toluene, and acetone. The hydrolysis–polycondensation of Ti4P3Ph proceeded in THF and toluene, while Ti4P3Ph in acetone proceeded in two paths (hydrolysis–polycondensation and nonhydrolysis–polycondensation). The hydrolyzed Ti4P3Ph retained its cluster structure, while the calcined Ti4P3Ph at 300°C contained a collapsed cluster structure. The specific surface areas of the hydrolyzed Ti4P3Ph in THF, toluene, and acetone were 154, 302, and 7 m2 g−1, respectively. The photodegradation ability of the hydrolyzed Ti4P3Ph for methylene blue was confirmed by ultraviolet irradiation at 365 nm; however, that of the calcined Ti4P3Ph was not. It was considered that the calcined Ti4P3Ph did not retain its cluster structure. The photocatalytic ability of the hydrolyzed Ti4P3Ph was high in the order of toluene > THF > pristine > acetone. The gels retained cluster structure have higher photocatalytic ability than pristine cluster; however, the gel contained a collapsed cluster structure was found no catalytic ability.

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Synthesis, characterization and properties of titanium phosphonate clusters

Cited by 14 publications

References 49 publications

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

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

Titanium phosphonate oxo-alkoxide “clusters”: solution stability and facile hydrolytic transformation into nano titania

Sol–gel reaction of titanium phosphonate alkoxide cluster

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