Unexpected Cyclopentadienyl/Alkoxo Ligand Exchange in Titano- and Zirconocene. New Opportunities

Sobota, Piotr; Utko, Józef; John, Łukasz; Jerzykiewicz, Lucjan B.; Drág-Jarzábek, Anna

doi:10.1021/ic8009749

Cited by 23 publications

(13 citation statements)

References 29 publications

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“…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%

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

et al. 2020

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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.

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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

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“…A similar, but neutral, Ti(III) complex [Cp 3 Ti 2 (μ-OEt) 2 (OEt)] was observed during our previous research on the reduction of Cp 2 TiCl 2 with metallic manganese in EtOH. 27 For 4−5 as well as for 3 within the Cp 2 Ti moiety, the angles subtended at the Ti atoms to the centroids of Cp rings are typical for this type of connection and ranges from 133.11(8)°t o 135.8(2)°. 28 Syntheses and Structures of Ti/In Compounds.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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

et al. 2017

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The aim of the current study was to examine the effects of group 13 metals on CpTiCl reduction in the presence of 2-methoxyethanol (MeOEtOH) or ethanol (EtOH) and the compositions of the resulting products. Direct reaction of CpTiCl and M [Al, Al (Fe contaminated), Ga, In] in toluene/alcohol for 2 h gave a new family of uncommon homo- and heterometallic compounds: [CpTiAl(μ,η-OEtOMe)Cl][Ti(μ,η-OEtOMe)(η-OEtOMe)Cl] (1), [CpTiAl(μ,η-OEtOMe)Cl]Cl (2), [CpTiAl(μ,η-OEtOMe)Cl][CpTi(η-HOEtOMe)][FeCl] (3), [CpTi(η-HOEtOMe)][GaCl][Cl] (4), [CpTi(μ-OEt)(OEt)][GaCl] (5), [CpTi(μ,η-OEtOMe)Cl] (6), and [CpTi(μ,η-OEtOMe)(μ-OEtOMe)Cl] (7). The reaction with indium for 48 h resulted in isolation of [TiIn(μ,η-OEtOMe)(OEtOMe)Cl] (8), [In(μ-OEtOMe)(HOEtOMe)Cl] (9), and [Ti(OEtOMe)] (10). The complexes were characterized using elemental analysis, IR and NMR spectroscopies, and, for 1-9, single-crystal X-ray diffraction. The use of metallic gallium and indium to reduce CpTiCl opens up a previously unexplored path that may provide access to novel and unique compounds.

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“…The observed sharp increase in the Ti(1)‐O(1) and Ti(1)‐C(1) distances in 4 indicates on a significant contribution of resonance forms 4 b , 4 c and 4 e to the electronic structure of the complex (see Scheme ). For other titanocene complexes containing comparable elongated Ti−O bonds, see, e. g., refs …”

Section: Resultsmentioning

confidence: 99%

Complexation of Titana‐ and Zirconadihydrofuran Metallacycles with Organoaluminium Compounds and Catalytic Activity of the Resulting Complexes in Polymerization of ϵ‐Caprolactone

et al. 2017

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The interaction of the titanadihydrofuran metallacycles Cp2Ti[η2‐C(SiMe3)=C(Ph)‐C(Me)2O] (1) and Cp2Ti[η2‐C(SiMe3)= C(Ph)‐CH(Ph)O] (2) with iBu2AlH in n‐hexane at 20°C yields 1 : 1 complexes Cp2Ti[η2‐C(SiMe3)=C(Ph)‐C(Me)2O](iBu2AlH) (4) and Cp2Ti[η2‐C(SiMe3)=C(Ph)‐CH(Ph)O](iBu2AlH) (5) respectively. According to X‐ray diffraction data, the iBu2AlH molecule in 4 is coordinated by its aluminium centre with the oxygen atom whereas the hydride hydrogen atom of the iBu2AlH forms a bridge with the titanium. As a result of the complexation with iBu2AlH, the Ti−O and Ti‐C(SiMe3) bonds of the starting 1 are strongly elongated. An analogous 1 : 1 adduct (11) is formed in the interaction of iBu2AlH with the zirconadihydrofuran derivative Cp2Zr[η2‐C(SiMe3)=C(SiMe3)‐C(Me)2O] (3). Like the Ti−O and Ti‐C(SiMe3) bonds in 1, the Zr−O and Zr‐C(SiMe3) bonds in 3 are considerably elongated as a result of the coordination with iBu2AlH. The reaction of 1 with EtAlCl2 gives a complex, Cp2Ti[η2‐C(SiMe3)=C(Ph)‐C(Me)2O](EtAlCl2) (8), in which the organoaluminium compound is also coordinated by its aluminium centre with the oxygen atom. This leads to a strong elongation of the Ti−O bond. The C−O bond of the metallacycle in 8 is noticeably elongated as well but the Ti‐C(SiMe3) bond length even somewhat shortens. Complexes 4, 5, 8 and 11 are capable of catalysing ring‐opening polymerization of ϵ‐caprolactone. The highest activity is exhibited by complexes 4 and 5.

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Unexpected Cyclopentadienyl/Alkoxo Ligand Exchange in Titano- and Zirconocene. New Opportunities

Cited by 23 publications

References 29 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

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

Complexation of Titana‐ and Zirconadihydrofuran Metallacycles with Organoaluminium Compounds and Catalytic Activity of the Resulting Complexes in Polymerization of ϵ‐Caprolactone

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Unexpected Cyclopentadienyl/Alkoxo Ligand Exchange in Titano- and Zirconocene. New Opportunities

Cited by 23 publications

References 29 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

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

Complexation of Titana‐ and Zirconadihydrofuran Metallacycles with Organoaluminium Compounds and Catalytic Activity of the Resulting Complexes in Polymerization of ϵ‐Caprolactone

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