85959-83-7

Basic information

• Product Name: BIS(PENTAMETHYLCYCLOPENTADIENYL)HAFNIUM DICHLORIDE
• Synonyms: Bis(pentamethylcyclopentadienyl)hafnium(iV) dichloride, 98+%;Bis(pentamethylcyclopentadienyl)hafnium dichloride, min. 98%;Bis(pentamethylcyclopentadienyl)hafnium dichloride,98%;BIS(PENTAMETHYLCYCLOPENTADIENYL)HAFNIUM DICHLORIDE;BIS(PENTAMETHYLCYCLOPENTADIENYL)HAFNIUM(IV) DICHLORIDE;Bis(pentamethylcyclopentadienyl)hafniumdichloride,min.98%;GFYKFLIFRXBFOR-UHFFFAOYSA-L
• CAS NO: 85959-83-7
• Molecular Formula: C₂₀H₃₀Cl₂Hf
• Molecular Weight: 519.85
• Product Categories: metallocene
• Mol File: 85959-83-7.mol
• Article Data: 3

Chemical Properties

• Melting Point: >300 °C(lit.)
• Appearance: white/crystal
• Density: >300
• Sensitive: moisture sensitive
• CAS DataBase Reference: BIS(PENTAMETHYLCYCLOPENTADIENYL)HAFNIUM DICHLORIDE(CAS DataBase Reference)
• NIST Chemistry Reference: BIS(PENTAMETHYLCYCLOPENTADIENYL)HAFNIUM DICHLORIDE(85959-83-7)
• EPA Substance Registry System: BIS(PENTAMETHYLCYCLOPENTADIENYL)HAFNIUM DICHLORIDE(85959-83-7)

Safety Data

• Hazard Codes: Xn
• Statements: 20/21/22-36/37/38
• Safety Statements: 26-36
• WGK Germany: 3
• TSCA: No
• Hazardous Substances Data: 85959-83-7(Hazardous Substances Data)

Usage

Chemical Properties

light yellow to yellow-beige crystals or

InChI:InChI=1/2C10H15.2ClH.Hf/c2*1-7-6-10(4,5)9(3)8(7)2;;;/h2*1-5H3;2*1H;/q;;;;+2/p-2/rC20H30Hf.2ClH/c1-11-13(3)17(19(7,8)15(11)5)21-18-14(4)12(2)16(6)20(18,9)10;;/h1-10H3;2*1H/q+2;;/p-2

Upstream product

• 116437-03-7 Cp'2Hf(OC₆F₅)2 
• 116437-01-5 Cp'2HfMe₂ 
• 92786-75-9 Cp'2HfI₂ 
• 75181-08-7 pentamethylcyclopentadienylhafnium trichloride 
• 51905-34-1 pentamethylcyclopentadienyllithium 
• 13499-05-3 hafnium tetrachloride 
• 109-72-8 n-butyllithium 
• 4045-44-7 1,2,3,4,5-pentamethylcyclopentadiene 

Downstream Products

• 184019-68-9 ((CH₃)5C₅)2Hf(CCC₆H₄CH₃)2 
• 217966-07-9 (η(5)-C5Me5)2Hf(SC6H5)2 
• 217966-12-6 (η(5)-C5Me5)2Hf(SC6H4OMe-p)2 
• 107681-83-4 (η5-C5Me5)2Hf(CH2C6H4-m-NMe2)2 
• 141272-80-2 (C₅(CH₃)5)2Hf(Si(C₆H₅)3)Cl 
• 107681-81-2 (η5-C5Me5)2Hf(CH2C6H5)2 
• 139042-55-0 (η5-C5Me5)2Hf(NH(2,4,6-Me3C6H2))2 
• 121055-48-9 (η-C5Me5)2Hf(Cl)(PH(c-C6H11)) 

Relevant articles and documents

Halide, hydride, alkyl, and dinitrogen complexes of bis(pentamethylcyclopentadienyl)hafnium

Bis(pentamethylcyclopentadienyl)hafnium dichloride (Cp*2HfCl2, Cp* = η5-C5Me5) is obtained by treatment of HfCl4 with lithium pentamethylcyclopentadienide in refluxing xylenes. The dioodide derivative is obtained from Cp*2HfCl2 with BI3. The dihydrido derivative is obtained via treatment of Cp*2HfCl2 with n-butyllithium under an atmosphere of H2. Treatment of Cp*2HfH2 with alkyl halides (RX) affords either Cp*2HfX2 or Cp*2HfHX and alkane depending on the nature of RX. The reaction of phenyllithium and Cp*2HfH2 provides a novel route to the phenyl hydride derivative Cp*2HfH(Ph). The variance of the chemical shift of the hydride with X for complexes of the type Cp*2HfH(X) (X = hydride, alkyl, alkenyl, aryl, halide, alkoxide, amide) is discussed in terms of paramagnetic shielding. The dinitrogen complex {Cp*2HfN2}2N2 is obtained in modest yield by Na/K reduction of Cp*2HfI2 and is isostructural with the zirconium analogue. Cp*2HfH2 forms an adduct with CO. Under high pressures of CO, reductive elimination of H2 and generation of Cp*2Hf(CO)2 is observed. Treatment of Cp*2Hf(CO)2 with H2 (3 atm) at 125°C cleanly affords Cp*2HfH(OCH3) and 1 equiv of CO; Cp*2Hf(CO)2 with Cp*2MH2 (M = Zr, Hf) under H2 yields cis-(Cp*2HfH)(Cp*2MH)(μ-OCH=CHO). Warming of Cp*2HfH2(CO) under H2 yields Cp*2HfH-(OCH3), cis-(Cp*2HfH)2(μ-OCH=CHO), trans-(Cp*2HfH)2(μ-OCH=CHO), and (Cp*2HfH)2(μ-OCH2CH2C). The relative yields of the individual products depend critically on reaction conditions, and the complexity of these reactions has thwarted all attempts to elucidate their mechanisms. Treatment of Cp*2HfH2 with olefins of the formula CH2=CRR′ or tert-butylacetylene gives alkyl hydrides Cp*HfH(CH2CHRR′) or the alkenyl hydride Cp*2HfH(CH=CHCMe3), which are very resistant to reductive elimination. Ethylene induces loss of alkane (CH3CHRRR′) or CH2=CHCMe3; however, with formation of the hafnacyclopentane derivative Cp*2Hf(CH2CH2CH2CH 2). Hydrogenation of the alkyl hydride complexes or Cp*2HfH(CH2= CHCMe3) affords Cp*2HfH2 and CH3CHRR′ or CH3CH2CMe3.

Erratum: Halide, hydride, alkyl, and dinitrogen complexes of bis(pentamethylcyclopentadienyl)hafnium (Organometallics (1985) 4, (97))

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