New titanium and zirconium sandwich and half-sandwich complexes containing the C5Me4CH2CH2CHCH2(Cp=) ligand

Butakoff, Kirill A.; Lemenovskii, D. A.; Mountford, Philip; Kuz'mina, L. G.; Churakov, Andrei V.

doi:10.1016/0277-5387(95)00234-j

Cited by 26 publications

(25 citation statements)

References 36 publications

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“…Contrarily, nearly all of the known solvent-free monocyclopentadienyl zirconium(IV) complexes, with even sterically crowded ones among them, exhibit a strong tendency to form double l-Cl bridges between Zr atoms and exist as dimers [6,[9][10][11][12][13][14]. Moreover, the coordination unsaturation of the Zr(IV) center is so explicit, that, in presence of the alkali metal chlorides, these dimers easily accept the third chlorine bridge atom to form complexes of general type [CpZrCl 2 -(l-Cl) 3 [15].…”

Section: X-ray Structural Investigations Of Zirconocene Dichloride 4 mentioning

confidence: 99%

Mono- and bis-(2-dimethylaminoethyl)tetramethylcyclopentadienyl zirconium(IV) complexes: synthesis and structural studies in crystalline state and in solutions

Krut’ko

Borzov

Kirsanov

et al. 2004

Journal of Organometallic Chemistry

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A novel half-sandwich Zr(IV) complex [g 5 :g 1 -N -C 5 (CH 3 ) 4 CH 2 CH 2 N(CH 3 ) 2 ]ZrCl 3 (6) together with zirconocene dichlorides [g 5 -C 5 (CH 3 ) 4 CH 2 CH 2 N(CH 3 ) 2 ][g 5 -C 5 (CH 3 ) 5 ]ZrCl 2 (4) and [g 5 -C 5 (CH 3 ) 4 CH 2 CH 2 N(CH 3 ) 2 ] 2 ZrCl 2 (5) have been prepared. Complex 6 has been isolated and characterized in three different forms, namely, as an adduct with THF 6a, an adduct with tetrahydrothiophene 6b, and a solvent-free form 6c. Molecular structures of complexes 4, 6b, and 6c have been established by X-ray diffraction analysis. Complex 6c has been shown to be a monomeric solvent-free half sandwich Zr(IV) complex. The dynamic behavior of complex 6a in a non-solvating medium (an equilibrium between 6a and 6c along with a degenerate interconversion of the Zr-C cp -CH 2 -CH 2 -N(CH 3 ) 2 -(Zr) pseudo-five-member metallacycle) have been studied by the variable-temperature 1 H and 13 C{ 1 H} NMR spectroscopy. The activation parameters for the degenerate five-member cycle interconversion have been elucidated.

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Section: X-ray Structural Investigations Of Zirconocene Dichloride 4 mentioning

confidence: 99%

Mono- and bis-(2-dimethylaminoethyl)tetramethylcyclopentadienyl zirconium(IV) complexes: synthesis and structural studies in crystalline state and in solutions

Krut’ko

Borzov

Kirsanov

et al. 2004

Journal of Organometallic Chemistry

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“…3). 12,19,20 21 The ring non-or mono-substituted compounds 9 and 10 lose pyridine in solution or the solid state forming mimido bridged dimers. However, the ring penta-substituted homologues 12-14 are stable to pyridine loss under comparable conditions.…”

Section: Half-sandwich Compoundsmentioning

confidence: 99%

New titanium imido chemistry

Mountford¹

1997

Chem. Commun.

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153

183

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“…It is known that LiCl can interact with the target half-sandwiches and form stable ionic products. [19] This complicates the isolation procedure, and in some cases high-vacuum sublimation is necessary for plained by the influence of the electron-donating effect of four methyl groups at the cyclopentadienyl ring. The the final purification of a metal complex.…”

Section: Resultsmentioning

confidence: 99%

A Novel Route to the 5-[2-(Diphenylphosphanyl)ethyl]-1,2,3,4-tetramethylcyclopentadienyl Ligand – Synthesis and Crystal Structure of [η5:η1-C5(CH3)4CH2CH2PPh2]ZrCl3·THF

Krut’ko¹,

Borzov

Veksler

et al. 1999

Eur. J. Inorg. Chem.

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The five‐step synthesis of the first transition metal complex with the C5(CH3)4CH2CH2PPh2 ligand [η5:η1‐C5(CH3)4CH2CH2PPh2]ZrCl3·THF (11), starting from the known compound [2‐(dimethylamino)ethyl]tetramethylcyclopentadiene (4) via 4,5,6,7‐tetramethylspiro[2,4]hepta‐4,6‐diene (7), is reported. Lithium cyclopentadienide LiC5(CH3)4CH2CH2PPh2 (9), silylated cyclopentadiene (CH3)3SiC5(CH3)4CH2CH2PPh2 (10) and cyclopentadiene HC5(CH3)4CH2CH2PPh2 (12) were isolated and characterised as pure substances. The crystal structure of the zirconium complex 11 was established by X‐ray diffraction analysis.

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New titanium and zirconium sandwich and half-sandwich complexes containing the C5Me4CH2CH2CHCH2(Cp=) ligand

Cited by 26 publications

References 36 publications

Mono- and bis-(2-dimethylaminoethyl)tetramethylcyclopentadienyl zirconium(IV) complexes: synthesis and structural studies in crystalline state and in solutions

Mono- and bis-(2-dimethylaminoethyl)tetramethylcyclopentadienyl zirconium(IV) complexes: synthesis and structural studies in crystalline state and in solutions

New titanium imido chemistry

A Novel Route to the 5-[2-(Diphenylphosphanyl)ethyl]-1,2,3,4-tetramethylcyclopentadienyl Ligand – Synthesis and Crystal Structure of [η5:η1-C5(CH3)4CH2CH2PPh2]ZrCl3·THF

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