(Cyclopentadienyl)titanium trichloride

(Cyclopentadienyl)titanium trichloride
Names
Other names
Titanocene trichloride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.156.156 Edit this at Wikidata
UNII
  • InChI=1S/C5H5.3ClH.Ti/c1-2-4-5-3-1;;;;/h1-5H;3*1H;/q;;;;+3/p-3
    Key: AENCLWKVWIIOQH-UHFFFAOYSA-K
  • c1[cH-]ccc1.Cl[Ti+](Cl)Cl
Properties
C5H5Cl3Ti
Molar mass 219.31 g·mol−1
Appearance orange solid
Density 1.768 g/cm3
Melting point 210 °C (410 °F; 483 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

(Cyclopentadienyl)titanium trichloride is an organotitanium compound with the formula (C5H5)TiCl3. It is a moisture sensitive orange solid. The compound adopts a piano stool geometry.[1]

Preparation and reactions

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(C5H5)TiCl3 is prepared by the reaction of titanocene dichloride and titanium tetrachloride:

(C5H5)2TiCl2 + TiCl4 → 2 (C5H5)TiCl3

The complex is electrophilic, readily forming alkoxide complexes upon treatment with alcohols.[2]

Reduction of (cyclopentadienyl)titanium trichloride with zinc powder gives the polymeric Ti(III) derivative (cyclopentadienyl)titanium dichloride:[3]

(C5H5)TiCl3 + 0.5 Zn → 1/n [(C5H5)TiCl2]n + ZnCl2

A related reduction can be effected with cobaltocene:[4]

(C5H5)TiCl3 + (C5H5)2Co → [(C5H5)2Co]+[(C5H5)TiCl3]

Other evidence for the Lewis acidity of the trichloride is the ready formation of adducts with phosphine ligands:[5]

(C5H5)TiCl3 + P(CH3)3 → (C5H5)TiCl3(P(CH3)3

See also

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References

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  1. ^ Rossini, A. J.; Mills, R. W.; Briscoe, G. A.; Norton, E. L.; et al. (2009). "Solid-State Chlorine NMR of Group IV Transition Metal Organometallic Complexes". Journal of the American Chemical Society. 131 (9): 3317–3330. doi:10.1021/ja808390a. PMID 19256569.
  2. ^ Andreas Hafner; Rudolf O. Duthaler (2001). "Trichloro(cyclopentadienyl)titanium". EEROS. doi:10.1002/047084289X.rt202m. ISBN 0-471-93623-5.
  3. ^ Lucas, C. R.; Green, M. L. H. (2007) [1976]. "Some η-Cyclopentadienyl Complexes of Titanium(III)". Inorganic Syntheses. Vol. 16. pp. 237–240. doi:10.1002/9780470132470.ch62. ISBN 978-0-470-13178-7.
  4. ^ Hughes, D.L.; Jimenez-Tenorio, M.; Leigh, G.J. (1989). "Synthesis of [Co(η5-C5H5)2][M(η5-C5H5)Cl3] salts (M = Ti or V): Crystal structure of [Co(η5-C5H5)2][Tc(η5-C5H5)Cl3]". Polyhedron. 8 (13–14): 1780–1781. doi:10.1016/S0277-5387(00)80641-5.
  5. ^ Nadasdi, T. Timothy; Stephan, Douglas W. (1993). "Radical Routes to Titanium(IV) Thiolate Complexes: Structure and Reactivity of ((η5--C5H5)TiIII and -TiIV Donor and Thiolate Derivatives". Inorganic Chemistry. 32 (26): 5933–5938. doi:10.1021/ic00078a008.
  6. ^ Morris, Robert J.; Shaw, Scott L.; Jefferis, Jesse M.; Storhoff, James J.; Goedde, Dean M. (1998). "Monoindenyltrichloride Complexes of Titanium(IV), Zirconium(IV), and Hafnium(IV)". Inorganic Syntheses. Vol. 32. pp. 215–221. doi:10.1002/9780470132630.ch36. ISBN 978-0-471-24921-4.