Titanocene dichloride

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Titanocene dichloride
Titanocene dichloride
Ball-and-stick model of titanocene dichloride
Sample of titanocene dichloride
Names
IUPAC name
Dichloridobis(η5-cyclopentadienyl)titanium
Other names
titanocene dichloride, dichlorobis(cyclopentadienyl)titanium(IV)
Identifiers
3D model (
JSmol
)
ChemSpider
ECHA InfoCard
 100.013.669 Edit this at Wikidata
EC Number
  • 215-035-9
RTECS number
  • XR2050000
UNII
UN number 3261
  • InChI=1S/2C5H5.2ClH.Ti/c2*1-2-4-5-3-1;;;/h2*1-5H;2*1H;/q2*-1;;;+4/p-2 ☒N
    Key: YMNCCEXICREQQV-UHFFFAOYSA-L ☒N
  • InChI=1/2C5H5.2ClH.Ti/c2*1-2-4-5-3-1;;;/h2*1-5H;2*1H;/q2*-1;;;+4/p-2/r2C5H5.Cl2Ti/c2*1-2-4-5-3-1;1-3-2/h2*1-5H;/q2*-1;+2
    Key: YMNCCEXICREQQV-JUFMQDBHAK
  • [cH-]1cccc1.[cH-]1cccc1.Cl[Ti+2]Cl
Properties
C10H10Cl2Ti
Molar mass 248.96 g/mol
Appearance bright red solid
Density 1.60 g/cm3, solid
Melting point 289 °C (552 °F; 562 K)
sl. sol. with hydrolysis
Structure
Triclinic
Dist. tetrahedral
Hazards[1]
GHS labelling:
GHS07: Exclamation mark
Warning
H315, H335
P201, P202, P261, P264, P270, P271, P280, P281, P301+P310, P301+P312, P302+P352, P304+P340, P305+P351+P338, P308+P313, P312, P330, P332+P313, P337+P313, P362, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability (red): no hazard codeInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
2
1
Related compounds
Related compounds
 Ferrocene
Zirconocene dichloride
Hafnocene dichloride
Vanadocene dichloride
Niobocene dichloride
Tantalocene dichloride
Molybdocene dichloride
Tungstenocene dichloride
TiCl4
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)

Titanocene dichloride is the

hydrolyzes in air.[2] It shows antitumour activity and was the first non-platinum complex to undergo clinical trials as a chemotherapy drug.[3]

Preparation and structure

The standard preparations of Cp2TiCl2 start with titanium tetrachloride. The original synthesis by Wilkinson and Birmingham, using sodium cyclopentadienide,[4] is still commonly used:[5]

2 NaC5H5 + TiCl4 → (C5H5)2TiCl2 + 2 NaCl

It can also be prepared by using freshly distilled cyclopentadiene rather than its sodium derivative:[6]

2 C5H6 + TiCl4 → (C5H5)2TiCl2 + 2 HCl

Focusing on the geometry of the Ti center, Cp2TiCl2 adopts a distorted

tetrahedral geometry (counting Cp as a monodentate ligand). The Ti-Cl distance is 2.37 Å and the Cl-Ti-Cl angle is 95°.[7]

Reactions

Halide replacement reactions

Cp2TiCl2 serves as a source of Cp2Ti2+. A large range of nucleophiles will displace chloride. With NaSH and with polysulfide salts, one obtains the sulfido derivatives Cp2Ti(SH)2 and Cp2TiS5.[8]

The Petasis reagent, Cp2Ti(CH3)2, is prepared from the action of methylmagnesium chloride[9] or methyllithium[10] on Cp2TiCl2. This reagent is useful for the conversion of esters into vinyl ethers.

The

Tebbe reagent Cp2TiCl(CH2)Al(CH3)2, arises by the action of 2 equivalents Al(CH3)3 on Cp2TiCl2.[11][12]

Reactions affecting Cp ligands

One Cp ligand can be removed from Cp2TiCl2 to give tetrahedral CpTiCl3. This conversion can be effected with TiCl4 or by reaction with SOCl2.[13]

The sandwich complex (Cycloheptatrienyl)(cyclopentadienyl)titanium is prepared by treatment of titanocene dichloride with lithium cycloheptatrienyl.[14]

Titanocene itself, TiCp2, is so highly reactive that it rearranges into a TiIII hydride

solvate structurally characterised by X-ray crystallography.[17] The same compound had been reported earlier by a lithium aluminium hydride reduction[18] and sodium amalgam reduction[19] of titanocene dichloride, and studied by 1H NMR[20] prior to its definitive characterisation.[15][16]

"Titanocene" is not Ti(C5H5)2, but rather this isomer with a fulvalene dihydride structure.[16][17]

Redox

Reduction with zinc gives the

dimer of bis(cyclopentadienyl)titanium(III) chloride in a solvent-mediated chemical equilibrium:[21][22]

Cp2TiCl2 is a precursor to TiII derivatives. Reductions have been investigated using Grignard reagent and alkyl lithium compounds. More conveniently handled reductants include Mg, Al, or Zn. The following syntheses demonstrate some of the compounds that can be generated by reduction of titanocene dichloride in the presence of π acceptor ligands:[23]

Cp2TiCl2 + 2 CO + Mg → Cp2Ti(CO)2 + MgCl2
Cp2TiCl2 + 2 PR3 + Mg → Cp2Ti(PR3)2 + MgCl2

benzyne complexes are known.[24] One family of derivatives are the titanocyclopentadienes.[25] Rosenthal's reagent, Cp2Ti(η2-Me3SiC≡CSiMe3), can be prepared by this method. Two structures are shown, A and B, which are both resonance contributors to the actual structure of Rosenthal's reagent.[26]

Titanocene equivalents react with alkenyl alkynes followed by carbonylation and hydrolysis to form bicyclic cyclopentadienones, related to the Pauson–Khand reaction.[27] A similar reaction is the reductive cyclization of enones to form the corresponding alcohol in a stereoselective manner.[28]

Reduction of titanocene dichloride in the presence of conjugated

1,3-butadiene gives η3-allyltitanium complexes.[29] Related reactions occur with diynes. Furthermore, titanocene can catalyze C–C bond metathesis to form asymmetric diynes.[25]

Titanocene dichloride as a photoredox catalyst to open epoxides in green light.[30]

Derivatives of (C5Me5)2TiCl2

Many analogues of Cp2TiCl2 are known. Prominent examples are the ring-methylated derivatives (C5H4Me)2TiCl2 and (C5Me5)2TiCl2.

Medicinal research

Titanocene dichloride was investigated as an anticancer drug. In fact, it was both the first non-platinum coordination complex and the first metallocene to undergo a clinical trial.[3][31]

References

  1. ^ "Summary of Classification and Labelling". Retrieved 5 December 2021.
  2. ^ Budaver, S., ed. (1989). The Merck Index (11th ed.). Merck & Co., Inc.
  3. ^
    ISBN 978-0-471-76113-6
    .
  4. doi:10.1021/ja01646a008
    .
  5. S2CID 248287682
    .
  6. ISBN 9780120311026
    .
  7. doi:10.1139/v75-228
    .
  8. ISBN 9780470132586
    .
  9. ^ Payack, J. F.; Hughes, D. L.; Cai, D.; Cottrell, I. F.; Verhoeven, T. R. (2002). "Dimethyltitanocene". Organic Syntheses. 79: 19.
  10. doi:10.1002/jlac.19626540103
    .
  11. ISBN 9780120311200
    .
  12. ^ Straus, D. A. (2000). "μ-Chlorobis(cyclopentadienyl)(dimethylaluminium)-μ-methylenetitanium". Encyclopedia of Reagents for Organic Synthesis. London: John Wiley.
  13. Chem. Ind. - London
    . 44: 288–289.
  14. S2CID 222351619
    .
  15. ^
    ISBN 9780323156479
    .
  16. ^
    ISBN 9788122412581
    .
  17. ^
    doi:10.1016/0022-328X(92)83204-U
    .
  18. S2CID 101189483
    .
  19. doi:10.1021/om00143a019
    .
  20. doi:10.1016/0022-328X(85)87293-4
    .
  21. ISBN 9780470132524. {{cite book}}: |journal= ignored (help
    )
  22. doi:10.1021/ja00233a051
    .
  23. ISBN 0471936235
    .
  24. doi:10.1021/cr00089a004
    .
  25. ^
    PMID 10673320
    .
  26. doi:10.1021/om0208570
    .
  27. doi:10.1021/ja990682u
    .
  28. doi:10.1021/ja954192n
    .
  29. PMID 11749307
    .
  30. PMID 32216162
    .
  31. PMID 28124046. Archived from the original
    (PDF) on 2018-07-19. Retrieved 2019-07-13.

Further reading
Retrieved from "https://en.wikipedia.org/w/index.php?title=Titanocene_dichloride&oldid=1211038881"