Bis(cyclopentadienyl)zirconium dichloride Property

Melting point:

242-245 °C(lit.)

Boiling point:

124-125°C/15mm

Flash point:

124-125°C/15mm

storage temp. 

Keep in dark place,Inert atmosphere,2-8°C

form 

Powder

color 

white to off-white

Water Solubility 

hydrolysis

Sensitive 

Air & Moisture Sensitive

Hydrolytic Sensitivity

4: no reaction with water under neutral conditions

Exposure limits

ACGIH: TWA 5 mg/m3; STEL 10 mg/m3
NIOSH: IDLH 25 mg/m3; TWA 5 mg/m3; STEL 10 mg/m3

CAS DataBase Reference

1291-32-3(CAS DataBase Reference)

NIST Chemistry Reference

Bis(cyclopentadienyl)zirconium dichloride(1291-32-3)

EPA Substance Registry System

Zirconocene dichloride (1291-32-3)

Safety

Hazard Codes 

Xi

Risk Statements 

36/37/38-34

Safety Statements 

26-36-45-36/37/39

RIDADR 

UN3261

WGK Germany 

3

RTECS 

ZH7525000

F 

8-10-21

TSCA 

Yes

HazardClass 

8

PackingGroup 

II

HS Code 

29319090

Hazard and Precautionary Statements (GHS)

Symbol(GHS)

Signal word

Warning

Hazard statements

H315Causes skin irritation

H319Causes serious eye irritation

H335May cause respiratory irritation

Precautionary statements

P261Avoid breathing dust/fume/gas/mist/vapours/spray.

P264Wash hands thoroughly after handling.

P264Wash skin thouroughly after handling.

P271Use only outdoors or in a well-ventilated area.

P280Wear protective gloves/protective clothing/eye protection/face protection.

P302+P352IF ON SKIN: wash with plenty of soap and water.

P305+P351+P338IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continuerinsing.

Bis(cyclopentadienyl)zirconium dichloride Chemical Properties,Usage,Production

Description

Bis(cyclopentadienyl)zirconium(IV) Dichloride or zirconocene dichloride is one of numerous organo-metallic compounds (also known as metalorganic, organo-inorganic and metallo-organic compounds) sold by American Elements under the trade name AE Organo-Metallics^TM. As is the case for other transition metal metallocenes, bis(cyclopentadienyl)zirconium(IV) dichloride is most often used as a catalyst.

Chemical Properties

Bis(cyclopentadienyl)zirconium dichloride is a white crystals. Soluble in polar organic solvents. Stable in dry air, very slowly hydrolyzes in moist air.

Uses

Bis(cyclopentadienyl)zirconium dichloride is used for for Stereoselective Glycosidation. It is also used in the catalyzed transamidation of primary amides with amines. Zirconocene dichloride can also be used to prepare the Negishi reagent,in oxidative cyclisation reactions. Other applications include it is used to promote greener amidations of carboxylic acids and amines in catalytic amounts. This technology avoids the requirement of preactivation of the carboxylic acid or use of coupling reagents.

Uses

Zirconocene Dichloride is the main catalyst for Kaminsky-type catalytic systems, which have high activity and isotropy for catalytic olefin polymerization, and catalytic olefin zwitterionization has also been reported in the literature. Zirconocene Dichloride is also the main component of Negishi's reagent, which can be used for the ring formation of intramolecular dienes and the ring formation of intermolecular alkynes and olefins. Rubber accelerator, component of a catalyst system for polymerization of vinyl monomers, curing agent for water-repellent silicone materials, agent for plating with zirconium.

Application

Used to promote greener amidations of carboxylic acids and amines in catalytic amounts. This technology avoids the requirement of preactivation of the carboxylic acid or use of coupling reagents.
Direct amide formation from unactivated carboxylic acids and amines.
Useful in the synthesis of a wide range of early-transition-metal complexes and organometallic compounds.

Preparation

Synthesis of zirconium dichlorodichloride
A stirring magnet was placed in a 500 mL three-necked flask, fitted with a constant pressure dropping funnel and reflux condenser, evacuated, and replaced with pure nitrogen three times. The flask was added with 50mL of toluene and 22.3g (0.1mol) of ZrCl4, and the suspension was made by turning on the stirring. Add the THF solution of sodium cyclopentadienylide to a constant pressure dropping funnel, add dropwise at room temperature, keep the reaction solution slightly boiling, after the dropwise addition, continue the reaction for 2h. Under the heating of oil bath at 50℃, evaporate the solvent under reduced pressure to obtain a yellow solid. Put the solid into a soxhlet extractor and extract with CHCl3. Most of the solvent in the extract was evaporated under reduced pressure, and the solid was precipitated after cooling and filtered. The product was washed with a small amount of CHCl3 and dried under vacuum, yielding 20.2g of white crystals, 69% yield.

Reactions

Reagent for the conversion of enynes to bicyclic cyclopentenones.
Precursor for the cyclization of dienes to cyclopentane and cyclohexane derivatives.
Precatalyst for the alkylation of olefins.
Precursor to zirconocene complexes of unsaturated organic molecules.
Catalyst for the coupling of alkoxymethyl-substituted styrene derivatives.
Reagent for the carboalumination-Claisen rearrangement-carbonyl addition cascade reaction.
Useful for the preparation of vinyl allenes.
Reagent for the alkynylation of epoxides.
Catalyst for the formation of carbocycles from cyclic enol ether.

General Description

This product has been enhanced for catalytic efficiency.

Air & Water Reactions

Bis(cyclopentadienyl)zirconium dichloride is extremely unstable when exposed to air. Decomposes in water .

Reactivity Profile

Bis(cyclopentadienyl)zirconium dichloride is incompatible with water, acids, bases, alcohols and halogens.

Hazard

Toxic by inhalation and skin contact, irritant to eyes and mucous membranes.

Fire Hazard

Flash point data for Bis(cyclopentadienyl)zirconium dichloride are not available, but Bis(cyclopentadienyl)zirconium dichloride is probably combustible.

Safety Profile

Poison by intraperitoneal route. Mutation data reported. When heated to decomposition it emits toxic fumes of Zr and Cl-.

Purification Methods

Recrystallise the dichloride from CHCl3 or xylene and dry it in a vacuum. 1H NMR (CDCl3) : 6.52 from Me4Si. Store it dry in the dark under N2. [Reid et al. Aust J Chem 18 173 1965, Beilstein 16 IV 1770.]