Bis(cyclopentadienyl)titanium(III) Chloride

Nugent, William A.

doi:10.1002/047084289x.rn00294

Cited by 3 publications

(3 citation statements)

References 53 publications

(24 reference statements)

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“…Ti(III) metalloradicals are powerful intermediates in synthetic chemistry. The radical ring-opening of epoxides is one of their archetypal transformation, as exemplified by the extensive utilization of titanocene(III) chloride (Cp 2 TiCl, Cp = cyclopentadienyl) in synthesis. − These species are also efficient at abstracting halogen-atoms, − and while their application in XAT-based transformations is largely based on thermal manifolds requiring stoichiometric reductants (e.g., Zn or Mn), applications in photochemistry and photocatalysis are receiving an increasing attention. − …”

Section: Applications Of Xat Reactivity In Synthetic Photocatalysismentioning

confidence: 99%

Applications of Halogen-Atom Transfer (XAT) for the Generation of Carbon Radicals in Synthetic Photochemistry and Photocatalysis

Hernández¹,

Constantin²,

2021

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The halogen-atom transfer (XAT) is one of the most important and applied processes for the generation of carbon radicals in synthetic chemistry. In this review, we summarize and highlight the most important aspects associated with XAT and the impact it has had on photochemistry and photocatalysis. The organization of the material starts with the analysis of the most important mechanistic aspects and then follows a subdivision based on the nature of the reagents used in the halogen abstraction. This review aims to provide a general overview of the fundamental concepts and main agents involved in XAT processes with the objective of offering a tool to understand and facilitate the development of new synthetic radical strategies.

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Section: Applications Of Xat Reactivity In Synthetic Photocatalysismentioning

confidence: 99%

Applications of Halogen-Atom Transfer (XAT) for the Generation of Carbon Radicals in Synthetic Photochemistry and Photocatalysis

Hernández¹,

Constantin²,

2021

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“…Reactions involving transformations of these compounds to Cp 2 Ti(III) and Cp 2 Ti(II) species, loss of the Cp ring, or replacement of halogen by other ligands are also important . The reduction of Cp 2 TiCl 2 with Al, Mn, and Zn in tetrahydrofuran (THF) leads to dimeric (Cp 2 TiCl) 2 active Nugent’s reagents for highly diastereoselective pinacol coupling reactions of aldehydes, epoxide opening to alkyl radicals, and other reactions . In most organometallic reactions of transition-metal complexes, the η 5 -Cp ligand is a spectator and stays tightly bound to the center throughout the reaction.…”

Section: Introductionmentioning

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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“…Since Tebbe’s reagent is known to exist in various forms in solution, potentially complicating the investigation, we synthesized the simplified analogue bis(cyclopentadienyl)titanium chloride (Cp 2 TiCl) to use for comparison. Cp 2 TiCl provides the same {100} shape control as Tebbe’s reagent (Figure S6) and is obtained by a straightforward reduction of Cp 2 TiCl 2 using Al foil. − We then compared the catalysts [Me 5 Cp] 2 TiCl 2 and [TbCp] 2 TiCl 2 to Cp 2 TiCl. The catalyst concentration was controllably varied while keeping all other reaction conditions the same.…”

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confidence: 99%

Facet Tunability of Aluminum Nanocrystals

et al. 2022

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Aluminum nanocrystals (Al NCs) with a welldefined size and shape combine unique plasmonic properties with high earth abundance, potentially ideal for applications where sustainability and cost are important factors. It has recently been shown that single-crystal Al {100} nanocubes can be synthesized by the decomposition of AlH 3 with Tebbe's reagent, a titanium-(IV) catalyst with two cyclopentadienyl ligands. By systematically modifying the catalyst molecular structure, control of the NC growth morphology is observed spectroscopically, as the catalyst stabilizes the {100} NC facets. By varying the catalyst concentration, Al NC faceted growth is tunable from {100} faceted nanocubes to {111} faceted octahedra. This study provides direct insight into the role of catalyst molecular structure in controlling Al NC morphology.

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Bis(cyclopentadienyl)titanium(III) Chloride

Cited by 3 publications

References 53 publications

Applications of Halogen-Atom Transfer (XAT) for the Generation of Carbon Radicals in Synthetic Photochemistry and Photocatalysis

Applications of Halogen-Atom Transfer (XAT) for the Generation of Carbon Radicals in Synthetic Photochemistry and Photocatalysis

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

Facet Tunability of Aluminum Nanocrystals

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Bis(cyclopentadienyl)titanium(III) Chloride

Cited by 3 publications

References 53 publications

Applications of Halogen-Atom Transfer (XAT) for the Generation of Carbon Radicals in Synthetic Photochemistry and Photocatalysis

Applications of Halogen-Atom Transfer (XAT) for the Generation of Carbon Radicals in Synthetic Photochemistry and Photocatalysis

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

Facet Tunability of Aluminum Nanocrystals

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