Crystal structure of (η
 5-pentamethylcyclopentadienyl)titanium(III)dichloride (THF), C14H23Cl2OTi

Oswald, Tim; Schmidtmann, Marc; Beckhaus, Rüdiger

doi:10.1515/ncrs-2015-0221

Cited by 5 publications

(12 citation statements)

References 12 publications

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“…The κ 2 ‐coordinated BH 4 groups agree with the long Ti⋅⋅⋅B distances of 2.389(4) and 2.402(3) Å when compared with that found (2.220(9) Å) for the κ 3 ‐BH 4 ligands of complex 4 [32] . The Ti−O bond length of 2.111(2) Å compares well with those found in other titanium(III) tetrahydrofuran adducts such as [Ti(η 5 ‐C 5 Me 5 )Cl 2 (thf)] (Ti−O=2.083(2) Å) [11,37] …”

Section: Resultssupporting

confidence: 81%

Low‐Valent Titanium Species Stabilized with Aluminum/Boron Hydride Fragments

Yélamos

Horno

Mena

et al. 2021

Chemistry A European J

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Low‐valent titanium species were prepared by reaction of [TiCp*X3] (Cp*=η5‐C5Me5; X=Cl, Br, Me) with LiEH4 (E=Al, B) or BH3(thf), and their structures elucidated by experimental and theoretical methods. The treatment of trihalides [TiCp*X3] with LiAlH4 in ethereal solvents (L) leads to the hydride‐bridged heterometallic complexes [{TiCp*(μ‐H)}2{(μ‐H)2AlX(L)}2] (L=thf, X=Cl, Br; L=OEt2, X=Cl). Density functional theory (DFT) calculations for those compounds reveal an open‐shell singlet ground state with a Ti−Ti bond and can be described as titanium(II) species. The theoretical analyses also show strong interactions between the Ti−Ti bond and the empty s orbitals of the Al atom of the AlH2XL fragments, which behave as σ‐accepting (Z‐type) ligands. Analogous reactions of [TiCp*X3] with LiBH4 (2 and 3 equiv.) in tetrahydrofuran at room temperature and at 85 °C lead to the titanium(III) compounds [{TiCp*(BH4)(μ‐X)}2] (X=Cl, Br) and [{TiCp*(BH4)(μ‐BH4)}2], respectively. The treatment of [TiCp*Me3] with 4 and 5 equiv. of BH3(thf) produces the diamagnetic [{TiCp*(BH3Me)}2(μ‐B2H6)] and paramagnetic [{TiCp*(μ‐B2H6)}2] complexes, respectively.

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Section: Resultssupporting

confidence: 81%

Low‐Valent Titanium Species Stabilized with Aluminum/Boron Hydride Fragments

Yélamos

Horno

Mena

et al. 2021

Chemistry A European J

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“…6a Indeed, Gambarotta and co-workers have demonstrated that [Ti( 5 -C5H5)Cl2(thf)1.5] crystallizes as an equimolar mixture of the four-and five-coordinate complexes [Ti( 5 -C5H5)Cl2(thf)] and [Ti( 5 -C5H5)Cl2(thf)2]. 36,37 As previously observed in several studies, 11-20 14 the tetrahydrofuran ligand in 4 is only weakly coordinated. Thus, once crystals of 4 are separated from the solution, the tetrahydrofuran is gradually lost within hours at room temperature to give the dinuclear compound 2.…”

Section: Resultsmentioning

confidence: 69%

The Puzzling Monopentamethylcyclopentadienyltitanium(III) Dichloride Reagent: Structure and Properties

et al. 2019

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Following the track of the useful titanocene [Ti( 5 -C5H5)2Cl] reagent in organic synthesis, the related half-sandwich titanium(III) derivatives [Ti( 5 -C5R5)Cl2] are receiving increasing attention in radical chemistry of many catalyzed transformations. However, the structure of the active titanium(III) species remains unknown in the literature. Herein, we describe the synthesis, crystal structure, and electronic structure of titanium( III) aggregates of composition [{Ti( 5 -C5Me5)Cl2}n]. The thermolysis of [Ti( 5 -C5Me5)Cl2Me] (1) in benzene or hexane at 180 ºC results in the clean formation of [{Ti( 5 -C5Me5)Cl(-Cl)}2] (2), methane and ethene. The treatment of 1 with excess pinacolborane in hexane at 65 ºC leads to a mixture of 2 and the paramagnetic trimer [{Ti( 5 -C5Me5)(-Cl)2}3] (3). The Xray crystal structures of compounds 2 and 3 show Ti-Ti distances of 3.267(1) and 3.219(12) Å, respectively. Computational studies (CASPT2//CASSCF and BS DFT methods) for dimer 2 reveal a singlet ground state and a relatively large singlet-triplet energy gap. Nuclear magnetic resonance (NMR) spectroscopy of 2 in aromatic hydrocarbon solutions and DFT calculations for several [{Ti( 5 -C5Me5)Cl2}n] aggregates are consistent with the existence of an equilibrium between the diamagnetic dimer [{Ti( 5 -C5Me5)Cl(-Cl)}2] and a paramagnetic tetramer [{Ti( 5 -C5Me5)(-Cl)2}4] in solution. In contrast, complex 2 readily dissolves in tetrahydrofuran to give a green-blue solution from which blue crystals of the mononuclear adduct [Ti( 5 -C5Me5)Cl2(thf)] (4) were grown.

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“…The Ti-Cl bond lengths in 7 and 9 of 2.3331 (3)-2.3804 (4) Å are also in the range of typical Ti-Cl bond lengths, e.g. Cp 2 TiCl 2 [2.367 (2) and 2.361 (1) Å ; Clearfield et al, 1975], Cp*TiCl 2 (thf) [thf is tetrahydrofuran; 2.3426 (2) and 2.3251 (6) Å ; Oswald et al, 2016], TiCl 3 py 3 -(NCy 2 ) [Cy is cyclohexyl; 2.3653 (5), 2.3393 (5) and 2.3023 (5) Å ; Adler et al, 2014] or other complexes (Kessler et al, 2013;Sassmannshausen & Baumgartner, 2008;Edwards et al, 1995); the bond lengths are also in accordance with the already published structure of 8 (Diekmann et al, 2006). As The molecular structure of complex 9.…”

Section: Figurementioning

confidence: 85%

Molecular structures of a series of substituted bis(η⁵-cyclopentadienyl)titanium dihalides Cp^R ₂TiX ₂ [X = F, Cl, Br and I; R = CHPh₂, CH(p-Tol)₂ and adamantyl]

Oswald

Lauterbach

Schmidtmann

et al. 2018

Acta Crystallogr C Struct Chem

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Metallocene dihalides and derivatives thereof are of great interest as precursors for catalysts in polymerization reactions, as antitumor agents and, due to their increased stability, as suitable starting materials in salt metathesis reactions and the generation of metallocene fragments. We report the synthesis and structural characterization of a series of eleven substituted bis(η-cyclopentadienyl)titanium dihalides, namely bis[η-1-(diphenylmethyl)cyclopentadienyl]difluoridotitanium(IV), [Ti(CH)F], bis{η-1-[bis(4-methylphenyl)methyl]cyclopentadienyl}difluoridotitanium(IV), [Ti(CH)F], and bis{η-1-[bis(adamantan-2-yl)methyl]cyclopentadienyl}difluoridotitanium(IV), [Ti(CH)F], together with the bromide and iodide analogues, and the chloride analogues of the diphenylmethyl and adamantyl complexes. These eleven complexes were prepared by the reaction of the corresponding bis(η:η-pentafulvene)titanium complexes with different hydrogen halides (Cl, Br and I). The titanocene fluorides become available via chloride-fluoride exchange reactions.

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Crystal structure of (η ⁵-pentamethylcyclopentadienyl)titanium(III)dichloride (THF), C₁₄H₂₃Cl₂OTi

Abstract: C14H 23 Cl 2 OTi, monoclinic, P21/c (no. 14), a = 12.3163 (7)

Cited by 5 publications

References 12 publications

Low‐Valent Titanium Species Stabilized with Aluminum/Boron Hydride Fragments

Low‐Valent Titanium Species Stabilized with Aluminum/Boron Hydride Fragments

The Puzzling Monopentamethylcyclopentadienyltitanium(III) Dichloride Reagent: Structure and Properties

Molecular structures of a series of substituted bis(η⁵-cyclopentadienyl)titanium dihalides Cp^R ₂TiX ₂ [X = F, Cl, Br and I; R = CHPh₂, CH(p-Tol)₂ and adamantyl]

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Crystal structure of (η 5-pentamethylcyclopentadienyl)titanium(III)dichloride (THF), C14H23Cl2OTi

Abstract: C14H 23 Cl 2 OTi, monoclinic, P21/c (no. 14), a = 12.3163 (7)

Cited by 5 publications

References 12 publications

Low‐Valent Titanium Species Stabilized with Aluminum/Boron Hydride Fragments

Low‐Valent Titanium Species Stabilized with Aluminum/Boron Hydride Fragments

The Puzzling Monopentamethylcyclopentadienyltitanium(III) Dichloride Reagent: Structure and Properties

Molecular structures of a series of substituted bis(η5-cyclopentadienyl)titanium dihalides Cp R 2TiX 2 [X = F, Cl, Br and I; R = CHPh2, CH(p-Tol)2 and adamantyl]

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Crystal structure of (η ⁵-pentamethylcyclopentadienyl)titanium(III)dichloride (THF), C₁₄H₂₃Cl₂OTi

Molecular structures of a series of substituted bis(η⁵-cyclopentadienyl)titanium dihalides Cp^R ₂TiX ₂ [X = F, Cl, Br and I; R = CHPh₂, CH(p-Tol)₂ and adamantyl]