Synthesis, structure, and solution behavior of 1-chloro-2,2-difluorovinyl titanocene derivatives: The first X-ray study of a titanium fluorovinyl compound and spectroscopic elucidation of the [Cp2TiMe(η2- CF2=CClH)] complex

Nicholas A. Barnes; Alan K. Brisdon; Ian R. Crossley; Robin G. Pritchard; John E. Warren

doi:10.1021/om0499254

Synthesis, structure, and solution behavior of 1-chloro-2,2-difluorovinyl titanocene derivatives: The first X-ray study of a titanium fluorovinyl compound and spectroscopic elucidation of the [Cp2TiMe(η2- CF2=CClH)] complex

Nicholas A. Barnes, Alan K. Brisdon, Ian R. Crossley, Robin G. Pritchard, John E. Warren

Research output: Contribution to journal › Article › peer-review

Abstract

The first early-transition-metal 1-chloro-2,2-difluorovinyl complexes [Cp2TiXccnCCl=CF2)2-n] (X = Cl, F; n = 0, 1) have been synthesized by the low-temperature reaction of Cp 2TiX2 (X = Cl, F) with (1-chloro-2,2-difluorovinyl)lithum, generated in situ from HCFC-133a (CF3-CH2C1) and n-butyllithium. The complexes have been characterized by spectroscopy and, in the case of [Cp2TiCl(CCl=CF2)], by single crystal X-ray diffraction, making this the first structurally characterized titanium-based fluorovinyl compound. The marked solution-phase instability of these materials has been explored in an attempt to identify key characteristics that might lead to stabilized systems. To this end, syntheses of the compounds [Cp*2TiFn-(CF=CF2)2-n] (n = 0, 1) and [Cp2TiMe(CCl=CF2)] have been reported and their stabilities investigated further. In the case of [Cp2TiMe(CCl=CF 2)], this has led to the spectroscopic characterization of the π-complex [Cp2TiMe(η2-CF2=CClH)] as an intermediate in the solution-phase decomposition pathway.

Original language	English
Pages (from-to)	2680-2685
Number of pages	5
Journal	Organometallics
Volume	23
Issue number	11
DOIs	https://doi.org/10.1021/om0499254
Publication status	Published - 24 May 2004

Keywords

Vinyl compounds Role: PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (halo, titanium complexes; prepn., crystal structure, and stability of chlorodifluorovinyl titanocene derivs.); Crystal structure; Molecular structure (of titanium bis(cyclopentadienyl) chlorodifluorovinyl chloro complex); Decomposition; Stability (prepn., crystal structure, and stability of chlorodifluorovinyl titanocene derivs.); Metallocenes Role: PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (titanocenes; prepn., crystal structure, and stability of chlorodifluorovinyl titanocene derivs.)

Access to Document

10.1021/om0499254

Fingerprint

Dive into the research topics of 'Synthesis, structure, and solution behavior of 1-chloro-2,2-difluorovinyl titanocene derivatives: The first X-ray study of a titanium fluorovinyl compound and spectroscopic elucidation of the [Cp2TiMe(η2- CF2=CClH)] complex'. Together they form a unique fingerprint.

CCDC 240757: Experimental Crystal Structure Determination
Barnes, N. A. (Contributor), Brisdon, A. (Contributor), Crossley, I. R. (Contributor), Pritchard, R. (Contributor) & Warren, J. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2004
DOI: 10.5517/cc82jc6, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc82jc6&sid=DataCite
Dataset

Cite this

Barnes, N. A., Brisdon, A. K., Crossley, I. R., Pritchard, R. G., & Warren, J. E. (2004). Synthesis, structure, and solution behavior of 1-chloro-2,2-difluorovinyl titanocene derivatives: The first X-ray study of a titanium fluorovinyl compound and spectroscopic elucidation of the [Cp2TiMe(η2- CF2=CClH)] complex. Organometallics, 23(11), 2680-2685. https://doi.org/10.1021/om0499254

@article{c558947944a246bb989895764500cfdd,

title = "Synthesis, structure, and solution behavior of 1-chloro-2,2-difluorovinyl titanocene derivatives: The first X-ray study of a titanium fluorovinyl compound and spectroscopic elucidation of the [Cp2TiMe(η2- CF2=CClH)] complex",

abstract = "The first early-transition-metal 1-chloro-2,2-difluorovinyl complexes [Cp2TiXccnCCl=CF2)2-n] (X = Cl, F; n = 0, 1) have been synthesized by the low-temperature reaction of Cp 2TiX2 (X = Cl, F) with (1-chloro-2,2-difluorovinyl)lithum, generated in situ from HCFC-133a (CF3-CH2C1) and n-butyllithium. The complexes have been characterized by spectroscopy and, in the case of [Cp2TiCl(CCl=CF2)], by single crystal X-ray diffraction, making this the first structurally characterized titanium-based fluorovinyl compound. The marked solution-phase instability of these materials has been explored in an attempt to identify key characteristics that might lead to stabilized systems. To this end, syntheses of the compounds [Cp*2TiFn-(CF=CF2)2-n] (n = 0, 1) and [Cp2TiMe(CCl=CF2)] have been reported and their stabilities investigated further. In the case of [Cp2TiMe(CCl=CF 2)], this has led to the spectroscopic characterization of the π-complex [Cp2TiMe(η2-CF2=CClH)] as an intermediate in the solution-phase decomposition pathway.",

keywords = "Vinyl compounds Role: PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (halo, titanium complexes; prepn., crystal structure, and stability of chlorodifluorovinyl titanocene derivs.); Crystal structure; Molecular structure (of titanium bis(cyclopentadienyl) chlorodifluorovinyl chloro complex); Decomposition; Stability (prepn., crystal structure, and stability of chlorodifluorovinyl titanocene derivs.); Metallocenes Role: PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (titanocenes; prepn., crystal structure, and stability of chlorodifluorovinyl titanocene derivs.)",

author = "Barnes, {Nicholas A.} and Brisdon, {Alan K.} and Crossley, {Ian R.} and Pritchard, {Robin G.} and Warren, {John E.}",

year = "2004",

month = may,

day = "24",

doi = "10.1021/om0499254",

language = "English",

volume = "23",

pages = "2680--2685",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "11",

}

Barnes, NA, Brisdon, AK, Crossley, IR, Pritchard, RG & Warren, JE 2004, 'Synthesis, structure, and solution behavior of 1-chloro-2,2-difluorovinyl titanocene derivatives: The first X-ray study of a titanium fluorovinyl compound and spectroscopic elucidation of the [Cp2TiMe(η2- CF2=CClH)] complex', Organometallics, vol. 23, no. 11, pp. 2680-2685. https://doi.org/10.1021/om0499254

Synthesis, structure, and solution behavior of 1-chloro-2,2-difluorovinyl titanocene derivatives: The first X-ray study of a titanium fluorovinyl compound and spectroscopic elucidation of the [Cp2TiMe(η2- CF2=CClH)] complex. / Barnes, Nicholas A.; Brisdon, Alan K.; Crossley, Ian R. et al.
In: Organometallics, Vol. 23, No. 11, 24.05.2004, p. 2680-2685.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Synthesis, structure, and solution behavior of 1-chloro-2,2-difluorovinyl titanocene derivatives: The first X-ray study of a titanium fluorovinyl compound and spectroscopic elucidation of the [Cp2TiMe(η2- CF2=CClH)] complex

AU - Barnes, Nicholas A.

AU - Brisdon, Alan K.

AU - Crossley, Ian R.

AU - Pritchard, Robin G.

AU - Warren, John E.

PY - 2004/5/24

Y1 - 2004/5/24

N2 - The first early-transition-metal 1-chloro-2,2-difluorovinyl complexes [Cp2TiXccnCCl=CF2)2-n] (X = Cl, F; n = 0, 1) have been synthesized by the low-temperature reaction of Cp 2TiX2 (X = Cl, F) with (1-chloro-2,2-difluorovinyl)lithum, generated in situ from HCFC-133a (CF3-CH2C1) and n-butyllithium. The complexes have been characterized by spectroscopy and, in the case of [Cp2TiCl(CCl=CF2)], by single crystal X-ray diffraction, making this the first structurally characterized titanium-based fluorovinyl compound. The marked solution-phase instability of these materials has been explored in an attempt to identify key characteristics that might lead to stabilized systems. To this end, syntheses of the compounds [Cp*2TiFn-(CF=CF2)2-n] (n = 0, 1) and [Cp2TiMe(CCl=CF2)] have been reported and their stabilities investigated further. In the case of [Cp2TiMe(CCl=CF 2)], this has led to the spectroscopic characterization of the π-complex [Cp2TiMe(η2-CF2=CClH)] as an intermediate in the solution-phase decomposition pathway.

AB - The first early-transition-metal 1-chloro-2,2-difluorovinyl complexes [Cp2TiXccnCCl=CF2)2-n] (X = Cl, F; n = 0, 1) have been synthesized by the low-temperature reaction of Cp 2TiX2 (X = Cl, F) with (1-chloro-2,2-difluorovinyl)lithum, generated in situ from HCFC-133a (CF3-CH2C1) and n-butyllithium. The complexes have been characterized by spectroscopy and, in the case of [Cp2TiCl(CCl=CF2)], by single crystal X-ray diffraction, making this the first structurally characterized titanium-based fluorovinyl compound. The marked solution-phase instability of these materials has been explored in an attempt to identify key characteristics that might lead to stabilized systems. To this end, syntheses of the compounds [Cp*2TiFn-(CF=CF2)2-n] (n = 0, 1) and [Cp2TiMe(CCl=CF2)] have been reported and their stabilities investigated further. In the case of [Cp2TiMe(CCl=CF 2)], this has led to the spectroscopic characterization of the π-complex [Cp2TiMe(η2-CF2=CClH)] as an intermediate in the solution-phase decomposition pathway.

KW - Vinyl compounds Role: PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (halo, titanium complexes; prepn., crystal structure, and stability of chlorodifluorovinyl titanocene derivs.); Crystal str

U2 - 10.1021/om0499254

DO - 10.1021/om0499254

M3 - Article

SN - 0276-7333

VL - 23

SP - 2680

EP - 2685

JO - Organometallics

JF - Organometallics

IS - 11

ER -

Synthesis, structure, and solution behavior of 1-chloro-2,2-difluorovinyl titanocene derivatives: The first X-ray study of a titanium fluorovinyl compound and spectroscopic elucidation of the [Cp2TiMe(η2- CF2=CClH)] complex

Abstract

Keywords

Access to Document

Fingerprint

Datasets

CCDC 240757: Experimental Crystal Structure Determination

Cite this