Hafnocene dichloride

Hafnocene dichloride
Names
Other names
bis(cyclopentadienyl)hafnium dichloride
Identifiers
CAS Number
  • 12116-66-4
3D model (JSmol)
  • Interactive image
ChemSpider
  • 10654717
ECHA InfoCard 100.031.967 Edit this at Wikidata
EC Number
  • 235-177-5
PubChem CID
  • 24942143
InChI
  • InChI=1S/2C5H5.2ClH.Hf/c2*1-2-4-5-3-1;;;/h2*1-3H,4H2;2*1H;/q2*-1;;;+4/p-2
    Key: IXKLRFLZVHXNCF-UHFFFAOYSA-L
  • C1C=CC=[C-]1.C1C=CC=[C-]1.[Cl-].[Cl-].[Hf+4]
Properties
Chemical formula
 C10H10Cl2Hf
Molar mass 379.58 g·mol−1
Appearance white solid
Melting point 230–233 °C (446–451 °F; 503–506 K)
Hazards
GHS labelling:[1]
Pictograms
 GHS05: CorrosiveGHS07: Exclamation mark
Danger
Hazard statements
 H314, H315, H319, H335
Precautionary statements
 P260, P261, P264, P264+P265, P271, P280, P301+P330+P331, P302+P352, P302+P361+P354, P304+P340, P305+P351+P338, P305+P354+P338, P316, P319, P321, P332+P317, P337+P317, P362+P364, P363, P403+P233, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references
Chemical compound

Hafnocene dichloride is the organohafnium compound with the formula (C5H5)2HfCl2. It is a white solid that is sparingly soluble in some organic solvents. The lighter homologues zirconacene dichloride and titanocene dichloride have received much more attention. While hafnocene is only of academic interest, some more soluble derivatives are precatalysts for olefin polymerization. Moreso than the Zr analogue, this compound is highly resistant to reduction.

It is prepared by a salt metathesis reaction from hafnium tetrachloride by salt metathesis:

2 NaC5H5 + HfCl4 → (C5H5)2HfCl2 + 2 NaCl

Derivatives

Hydrolysis gives the trimer [(C5H5)2HfO]3.[2]

The chloride ligands can be replaced by other halides.[3]

The bis(phosphide) (C5H5)2Hf(PR2)2 can be prepared by salt metathesis from hafnocene dichloride.[4]

References

  1. ^ "Hafnocene dichloride". pubchem.ncbi.nlm.nih.gov.
  2. ^ Rogers, Robin D.; Vann Bynum, R.; Atwood, Jerry L. (1982). "Synthesis and Crystal Structure of [(η5-C5H5)2HfO]3C6H5Me". Journal of Crystallographic and Spectroscopic Research. 12 (3): 239–244. doi:10.1007/BF01195715. S2CID 97164127.
  3. ^ Druce, P. M.; Kingston, B. M.; Lappert, M. F.; Spalding, T. R.; Srivastava, R. C. (1969). "Metallocene Halides. Part I. Synthesis, Spectra, and Redistribution Equilibria of di-π-Cyclopentadienyldihalogeno-Titanium(IV),-Zirconium-(IV), and -Hafnium(IV)". J. Chem. Soc. A: 2106–2110. doi:10.1039/J19690002106.
  4. ^ Baker, R. T.; Whitney, J. F.; Wreford, S. S. (1983). "Characterization and Interconversion of Metal-Phosphorus Single and Double bonds: Bis(cyclopentadienyl)zirconium and -Hafnium Bis(diorganophosphide) Complexes". Organometallics. 2 (8): 1049–1051. doi:10.1021/om50002a022.
  • v
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Salts and covalent derivatives of the Cyclopentadienide ion
CpH He
LiCp Be B CpMe N C5H4O F Ne
NaCp MgCp2

MgCpBr

Al Si P S Cl Ar
K CaCp2 ScCp3 TiCp2Cl2

(TiCp2Cl)2
TiCpCl3
TiCp2S5
TiCp2(CO)2
TiCp2Me2

VCp2

VCpCh
VCp2Cl2
VCp(CO)4

CrCp2

(CrCp(CO)3)2

MnCp2 FeCp2

Fe(η5-C5H4Li)2
((C5H5)Fe(C5H4))2
(C5H4-C5H4)2Fe2
FeCp2PF6
FeCp(CO)2I

CoCp2

CoCp(CO)2

NiCp2

NiCpNO

Cu Zn Ga Ge As Se Br Kr
Rb Sr Y(C5H5)3 ZrCp2Cl2

ZrCp2ClH

NbCp2Cl2 MoCp2H2

MoCp2Cl2
(MoCp(CO)3)2

Tc RuCp2

RuCp(PPh3)2Cl
RuCp(MeCN)3PF6

RhCp2 PdCp(C3H5) Ag Cd InCp SnCp2 Sb Te I Xe
Cs Ba * LuCp3 HfCp2Cl2 Ta (WCp(CO)3)2 ReCp2H OsCp2 IrCp2 Pt Au Hg TlCp PbCp2 Bi Po At Rn
Fr Ra ** Lr Rf Db Sg Bh HsCp2 Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
 
* LaCp3 CeCp3 PrCp3 NdCp3 PmCp3 SmCp3 Eu Gd Tb DyCp3 Ho ErCp3 TmCp3 YbCp3
** Ac ThCp3
ThCp4 		Pa UCp4 Np Pu Am Cm Bk Cf Es Fm Md No