Synthesis of titanium-oxo macrocyles and their catalytic properties for oxidative desulfurization

Lv, Haiting; Cui, Ying; Zou, Guo-Dong; Li, Na; Yang, Pei; Fan, Yang

doi:10.1039/c9dt03057c

Cited by 17 publications

(12 citation statements)

References 33 publications

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“…Ti 14 O 19 (OH)(O t Bu) 13 (OAc) 4 [113] and Ti 17 O 24 (O i Pr) 18 (O 2 C−C 6 H 4 NMe 2 ) 2 (R’=CH=CHPh, CH=CH−C 6 H 4 NMe 2 , C 6 H 4 NMe 2 , C 5 H 4 N) [114] . The structure of Ti 18 O 25 (O t Bu) 12 (OAc) 10 [113] can be derived by condensing the core of the Ti 14 cluster with a Ti 4 unit. In Ti 32 O 16 (OCH 2 CH 2 O) 32 (OR) 16 (O 2 CR’) 16 (OR=OCH 2 CH 2 OH; R’=Et, iso ‐allyl, t Bu, [115] Pr, CMe 2 Et [116] ) (Figure 13, right), eight tetranuclear subunits are connected with each other (= [Ti 4 O 2 (OCH 2 CH 2 O) 4 (OR) 2 (O 2 CR’) 2 ] 8 ). The linkage of the [TiO x ] polyhedra within the tetranuclear subunits is similar to that in Ti 4 O 2 (OR) 10 (O 2 CR’) 2 (Figure 2).…”

Section: Carboxylato‐substituted Titanium Oxo Clustersmentioning

confidence: 99%

“… [114] The structure of Ti 18 O 25 (O t Bu) 12 (OAc) 10 [113] can be derived by condensing the core of the Ti 14 cluster with a Ti 4 unit. In Ti 32 O 16 (OCH 2 CH 2 O) 32 (OR) 16 (O 2 CR’) 16 (OR=OCH 2 CH 2 OH; R’=Et, iso ‐allyl, t Bu, [115] Pr, CMe 2 Et [116] ) (Figure 13 , right), eight tetranuclear subunits are connected with each other (= [Ti 4 O 2 (OCH 2 CH 2 O) 4 (OR) 2 (O 2 CR’) 2 ] 8 ). The linkage of the [TiO x ] polyhedra within the tetranuclear subunits is similar to that in Ti 4 O 2 (OR) 10 (O 2 CR’) 2 (Figure 2 ).…”

Section: Carboxylato‐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: Carboxylato‐substituted Titanium Oxo Clustersmentioning

confidence: 99%

Section: Carboxylato‐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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“…The efficient catalytic oxidation of bulky thiophene derivatives such as DBT and 4,6-DMDBT is crucial for the deep oxidative desulfurization (ODS) to produce ultra-low-sulfur fuels. [34][35][36][37][38][39][40][41][42][43] The size effect on the catalytic activity of MIL-125 was evaluated by oxidative desulfurization of DBT and 4,6-DMDBT. As shown in Fig.…”

Section: Papermentioning

confidence: 99%

Size modulation of MIL-125 nanocrystals to promote the catalytic performance towards oxidative desulfurization

ZongWen

Zhang

et al. 2021

Dalton Trans.

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“…[ 48 ] The number of Ti atoms in Ti–oxo clusters ranges from 3 to 32, including Ti 3 , [ 49–52 ] Ti 4 , [ 50,52–57 ] Ti 5 , [ 57 ] Ti 6 , [ 51,52,54,55,57–64 ] Ti 7 , [ 57 ] Ti 8 , [ 54,64,65 ] Ti 9 , [ 51,55,63 ] Ti 10 , [ 66 ] Ti 11 , [ 54–56,63 ] Ti 12 , [ 57,62,66,67 ] Ti 14 , [ 50,56 ] Ti 16 , [ 54,55,61,66 ] Ti 18 , [ 51,57 ] Ti 19 , [ 63 ] Ti 20 , [ 66,68 ] and Ti 32 clusters. [ 69 ] In general, during the assembly of Ti–oxo clusters, it is vital to control the competition between acids and coordinating ligands. By adjusting acidity, a controlled hydrolysis and nucleation of Ti sources can be established, leading to a cluster with a certain size.…”

Section: Cluster Chemistry Of Group 3 and 4 Metalsmentioning

confidence: 99%

Metal–Organic Frameworks Based on Group 3 and 4 Metals

et al. 2020

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Metal-organic frameworks (MOFs), a class of porous crystalline framework materials, are linked by strong bonds between inorganic and organic building blocks. [1-3] In the past two decades, MOFs have rapidly grown as a star material due to their exceptional performance in areas such as storage, separation and catalysis. [4] The outstanding performance of MOFs in applications benefits from their intrinsically porous structures and highly tunable pore environment. [5-7] The creation and modification of pore space with optimized size, functionality and diversity can be precisely tuned at the molecular level by rationally designing building blocks and synthetic procedures. [8,9] The diversity of MOFs can be enriched by expanding the library of organic linkers with varying lengths, geometries, and functional groups. [10] Additionally, very diverse metal cations are applied to MOF synthesis, ranging from monovalent (Ag + , Cu + , etc.), divalent (Mg 2+ , Fe 2+ , Co 2+ , Ni 2+ , etc.), trivalent (Al 3+ , Sc 3+ , V 3+ , Cr 3+ , etc.), to tetravalent (Ti 4+ , Zr 4+ , Hf 4+ , etc.) cations. [11] In this review, we mainly focus on MOFs with group 3 and 4 metals, including Y, lanthanides (Ln, from La to Lu), actinides (An, from Ac to Lr), Ti, and Zr (Figure 1). Group 3 metal cations are generally found in the oxidation state of +3 in the MOF structures, while group 4 metal cations mainly exist in the oxidation state of +4, leading to the formation of much stronger coordination bonds with carboxylates. [12] Therefore, group 4 metal-based MOFs (M IV-MOFs) generally have enhanced stability compared with MOFs constructed from metals of group 3 and other groups. This series of MOFs stands out because the involved metals can generally coordinate with carboxylates to form frameworks with strong coordination bonds, according to the Pearson's hard/soft acid/base principle, where group 3 and 4 metal cations are regarded as hard acids while carboxylate ligands are hard bases. [11] One remarkable feature of MOFs with group 3 and 4 metals is that they generally can form phases containing M 6 O 8 (M = Y, Ln, An, Zr and Hf) clusters, regardless of their atomic numbers, charges and radius. This series of M 6-based MOFs is best represented by UiO series such as UiO-66 with fcu topology. [13] Under different synthetic conditions, UiO-66(M, M = An, Zr and Hf) constructed from [M 6 (μ 3-O) 4 (μ 3-OH) 4 ] clusters and linear carboxylates can be obtained, while UiO-66(M, M = Y, Ln) is assembled from Metal-organic frameworks (MOFs) based on group 3 and 4 metals are considered as the most promising MOFs for varying practical applications including water adsorption, carbon conversion, and biomedical applications. The relatively strong coordination bonds and versatile coordination modes within these MOFs endow the framework with high chemical stability, diverse structures and topologies, and interesting properties and functions. Herein, the significant progress made on this series of MOFs since 2018 is summarized and an update on the current status an...

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Synthesis of titanium-oxo macrocyles and their catalytic properties for oxidative desulfurization

Abstract: Titanium-oxo macrocycles with an inner cavity of about 1.2 × 1.2 nm were synthesized and structurally characterized. The structure-dependent catalytic properties towards oxidative desulfurization were studied.

Cited by 17 publications

References 33 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

Size modulation of MIL-125 nanocrystals to promote the catalytic performance towards oxidative desulfurization

Metal–Organic Frameworks Based on Group 3 and 4 Metals

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