Impact of Group 13 Metals on Cp<sub>2</sub>TiCl<sub>2</sub> Reduction and Structural Characterization of Resulting Compounds

Petrus, Rafał; Utko, Józef; Lis, Tadeusz; Sobota, Piotr

doi:10.1021/acs.inorgchem.6b02824

Cited by 6 publications

(4 citation statements)

References 91 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, in both cases, unsymmetric dinuclear titanium compounds, namely, [Cp 3 Ti 2 (μ-OEt) 2 (OEt)] or [Cp 3 Ti 2 (μ,η 2 -OR)(μ-OR)Cl], were obtained. 39,40 The Ti1 atom is surrounded by two Cp rings, and the two oxygen atoms of the alkoxo ligand adopt a distorted tetrahedral geometry, similarly to coordination of a Zn1 atom by two Cl − anions and two oxygen donors from THF and the OR ligand. In the Cp 2 Ti group, the angle between the Ti1 atom and centroids of the Cp rings (Cg) is typical for this type of connection (i.e., 134.10(6)°).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The formation of Cp 2 Ti(OR) species was observed in our previous studies when metallic indium or manganese was used for the reduction of Cp 2 TiCl 2 in the presence of ethanol or 2-methoxyethanol. However, in both cases, unsymmetric dinuclear titanium compounds, namely, [Cp 3 Ti 2 (μ-OEt) 2 (OEt)] or [Cp 3 Ti 2 (μ,η 2 -OR)(μ-OR)Cl], were obtained. , …”

Section: Results and Discussionmentioning

confidence: 99%

See 1 more Smart Citation

Convenient Route to Heterometallic Group 4–Zinc Precursors for Binary Oxide Nanomaterials

et al. 2020

Self Cite

View full text Add to dashboard Cite

In this study, simple and efficient synthetic routes to a family of uncommon group 4−zinc heterometallic alkoxides were developed. Single-source molecular precursors with the structures [Cp 2 TiZn(μ,η-OR)(THF)Cl 2 ] (1), [Zr 3 Zn 7 (μ 3 -O)-(μ 3 ,η 2 -OR) 3 (μ-OH) 3 (μ,η 2 -OR) 6 (μ,η-OR) 6 Cl 6 ] (2), and [Hf 3 Zn 7 (μ 3 -O)(μ 3 ,η 2 -OR) 3 (μ-OH) 3 (μ,η 2 -OR) 6 (μ,η-OR) 6 Cl 6 ] (3) were prepared via reduction of Cp 2 TiCl 2 with metallic zinc or protonolysis of the metal−cyclopentadienyl bond in Cp 2 M′Cl 2 (M′ = Zr or Hf) in the presence of 2-methoxyethanol (ROH) and Zn(OR) 2 . This synthetic route enables the creation of compounds with well-defined molecular structures and therefore provides precursors suitable for obtaining group 4−zinc oxides. Precursors 1−3 were characterized by elemental analysis, nuclear magnetic resonance and infrared spectroscopies, and single-crystal X-ray diffraction. Compound 1 decomposed at 800−900 °C to give a mixture of binary metal oxides (i.e., Zn 2 Ti 3 O 8 , ZnTiO 3 , or Zn 2 TiO 4 ) and common polymorphs of TiO 2 and ZnO. After calcination at 1000 °C, only TiO 2 and the high-temperature-stable phase Zn 2 TiO 4 were observed. Thermolysis of compounds 2 and 3 gave mixtures of ZnO and ZrO 2 or HfO 2 , respectively. The obtained ZnO−ZrO 2 and ZnO−HfO 2 mixed oxide materials have constant phase compositions across a broad temperature range and therefore are attractive host lattices for Eu 3+ for applications as yellow/red double-light-emitting phosphors. It was established that Eu 3+ ions were successfully introduced into the ZnO and ZrO 2 /HfO 2 lattices. It was revealed that Eu 3+ ions prefer to occupy low-symmetry sites in ZrO 2 /HfO 2 rather than in ZnO.

show abstract

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

Convenient Route to Heterometallic Group 4–Zinc Precursors for Binary Oxide Nanomaterials

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

“…The reduced Cp 2 Ti(III)Cl plays dual roles in the present strategy for the formation of colloidal assemblies of Pd(0)–[CpPd(II)Cl] 2 NPs. First, it served as a reducing agent , in the formation of Pd NPs without adding additional reductant. Meanwhile, the in situ transmetalated-surface ligand [CpPd(II)Cl] 2 acted as “sticky bonds” for Pd(0) NPs that spontaneously self-assembled into colloidal metal–organic ligand networks.…”

Section: Resultsmentioning

confidence: 99%

Pd Nanoparticles Capped with [CpPd(II)Cl]₂ Complexes for Hydrogenation and Acid-Free Acetalization of α,β-Unsaturated Aldehydes

Zhao

Zhou

et al. 2019

ACS Appl. Nano Mater.

View full text Add to dashboard Cite

Hierarchical bottom-up self-assembly of nanoparticles by wet chemistry methods is a promising approach to the preparation of engineered metal–ligand networks with advanced catalytic properties. Here, we developed a facile strategy to synthesize self-organized metal–ligand Pd(0)–[CpPd(II)Cl]2 nanoreactor through a redox and in situ transmetalation reaction between palladium ions and titanium ions. The obtained integrated metallic Pd(0) nanoparticles with organic [CpPd(II)Cl]2 capping ligands have been systematically characterized. The self-assemblies can not only serve as a support providing physical barriers against aggregation of ultrasmall Pd nanoparticles with good stability while keeping Pd nanoparticle core highly accessible but can also act as an efficient bifunctional nanoreactor for the first realization of selective hydrogenation and acid-free acetalization cascade reaction. Because of the combination of the two functions of metallic Pd(0) nanoparticles and Lewis acid Pd(II) ions in the [CpPd(II)Cl]2 ligands, the obtained integrated Pd(0)–[CpPd(II)Cl]2 nanoreactor exhibits excellent hydrogenation selectivity and activity (up to 66%–98% yield) in the synthesis of the acetal derivatives from broad substrates of α,β-unsaturated aldehydes and alcohols under mild conditions. Our work has successfully engineered a metal–ligand ensemble to obtain an attractive bifunctional heterogeneous catalyst for cascade organic transformations, presenting a significant step toward the attainment of green and sustainable chemical reactions.

show abstract

“…In coordination, chemistry is many examples of metal compounds formed haphazardly by the action of impurities or additives (stabilizers, antioxidants, reductants) present in solvents, organic reagents, and a wide range of various metal precursors. [47][48][49] For example, Mg n Bu 2 , a convenient reagent used in organic synthesis or for the preparation of various magnesium compounds, contains up to 1 wt% of AlEt 3 as a viscosity reducer. The presence of AlEt 3 in the heptane solution of Mg n Bu 2 is generally imperceptible.…”

Section: Dalton Transactions Papermentioning

confidence: 99%

Use of heterometallic alkali metal–magnesium aryloxides in ring-opening polymerization of cyclic esters

2022

Self Cite

View full text Add to dashboard Cite

show abstract

Impact of Group 13 Metals on Cp₂TiCl₂ Reduction and Structural Characterization of Resulting Compounds

Cited by 6 publications

References 91 publications

Convenient Route to Heterometallic Group 4–Zinc Precursors for Binary Oxide Nanomaterials

Convenient Route to Heterometallic Group 4–Zinc Precursors for Binary Oxide Nanomaterials

Pd Nanoparticles Capped with [CpPd(II)Cl]₂ Complexes for Hydrogenation and Acid-Free Acetalization of α,β-Unsaturated Aldehydes

Use of heterometallic alkali metal–magnesium aryloxides in ring-opening polymerization of cyclic esters

Contact Info

Product

Resources

About

Impact of Group 13 Metals on Cp2TiCl2 Reduction and Structural Characterization of Resulting Compounds

Cited by 6 publications

References 91 publications

Convenient Route to Heterometallic Group 4–Zinc Precursors for Binary Oxide Nanomaterials

Convenient Route to Heterometallic Group 4–Zinc Precursors for Binary Oxide Nanomaterials

Pd Nanoparticles Capped with [CpPd(II)Cl]2 Complexes for Hydrogenation and Acid-Free Acetalization of α,β-Unsaturated Aldehydes

Use of heterometallic alkali metal–magnesium aryloxides in ring-opening polymerization of cyclic esters

Contact Info

Product

Resources

About

Impact of Group 13 Metals on Cp₂TiCl₂ Reduction and Structural Characterization of Resulting Compounds

Pd Nanoparticles Capped with [CpPd(II)Cl]₂ Complexes for Hydrogenation and Acid-Free Acetalization of α,β-Unsaturated Aldehydes