37342-97-5

Basic information

• Product Name: Bis(cyclopentadienyl)zirconium chloride hydride
• Synonyms: ZIRCONOCENE CHLORIDE HYDRIDE;Di(cyclopentadienyl)zirconium(IV) chloride hydride;bis(3-cyclopentadienyl)chlorohydrurozirconium;Bis(cyclopentadienyl)zirconium chloride hydride (Schwartz's Reagent),;Bis(cyclopentadienyl)zirconiumchloridehydride~Schwartz'sReagent~Zirconocenehydrochloride;Zirconocenechloridehydride,95%;Bis(cyclopentadienyl)zirconiumchloridehydride(Schwartz'sReagent),95%;Di(cyclopentadienyl)zirconium(IV) chloride hydride, Schwartz reagent, Zirconocene chloride hydride
• CAS NO: 37342-97-5
• Molecular Formula: C10H11ClZr
• Molecular Weight: 257.87
• EINECS: 253-479-5
• Product Categories: Zr;Classes of Metal Compounds;Metallocenes;Reduction;Synthetic Organic Chemistry;Titanocene, etc.;Transition Metal Compounds;Zr (Zirconium) Compounds;Auxiliaries,Catalysts
• Mol File: 37342-97-5.mol
• Article Data: 0

Chemical Properties

• Melting Point: 300 °C
• Boiling Point: 41.5ºC at 760 mmHg
• Appearance: off-white/Powder
• Vapor Pressure: 418mmHg at 25°C
• Storage Temp.: 2-8°C
• Water Solubility: reacts
• Sensitive: Light, Air & Moisture Sensitive
• Merck: 14,8396
• CAS DataBase Reference: Bis(cyclopentadienyl)zirconium chloride hydride(CAS DataBase Reference)
• NIST Chemistry Reference: Bis(cyclopentadienyl)zirconium chloride hydride(37342-97-5)
• EPA Substance Registry System: Bis(cyclopentadienyl)zirconium chloride hydride(37342-97-5)

Safety Data

• Hazard Codes: F,C
• Statements: 11-15-34
• Safety Statements: 16-26-27-36/37/39-8-45
• RIDADR: UN 3131 4.3/PG 2
• WGK Germany: 3
• F: 8-10-23
• HazardClass: 4.3
• PackingGroup: II
• Hazardous Substances Data: 37342-97-5(Hazardous Substances Data)

Usage

Reaction

Reagent for the hydrozirconation of olefins. Reagent for the hydrozirconation of alkynes. Catalyst for the hydroboration of olefins. Mediates the reduction of tertiary amides to aldehydes, without reduction of cyano, nitro, ester, or α,β-unsaturated groups. Catalyst for the asymmetric vinylation and dienylation of ketones. Useful reagent for dimethylzinc mediated additions alkenylzirconocenes to aldimines. Useful reagent for the synthesis of oxidized amides from nitriles. Reagent for the hydrozirconation of propargylic alcohols.

Chemical Properties

white to beige powder

Uses

Different sources of media describe the Uses of 37342-97-5 differently. You can refer to the following data:
1. Functionalization of unsaturated systems via an organozirconium intermediate.
2. Bis(cyclopentadienyl)zirconium hydridochloride is used in the conversion of amides to aldehydes. It is also used as a pharmaceutical intermediate.

Purification Methods

It is moisture and light sensitive. Determine its purity by reaction with a slight excess of Me2CO whereby the active H reacts to produce Cp2ZrClOPri and the integrals of the residual Me2CO in the 1H NMR will show its purity. The presence of Cp2ZrH2 can be determined because it forms Cp2Zr(OPri)2. For a very active compound, it is best to prepare it freshly from the dichloride (see below) by reduction with Vitride [LiAl(OCH2CH2OH)2H2], the white precipitate is filtered off, washed with tetrahydrofuran, then Et2O and dried in a vacuum. Store it dry in the dark. [Carr & Schwartz J Am Chem Soc 101 3521 1979, Negishi & Takahashi Synthesis 1 1988, Beilstein 16 IV 1770.]

InChI:InChI=1/2C5H.ClH.Zr.H/c2*1-2-4-5-3-1;;;/h2*1H;1H;;/q2*-5;;+1;/p-1/r2C5H.ClHZr/c2*1-2-4-5-3-1;1-2/h2*1H;2H/q2*-5;

Synthetic route

dicyclopentadienylzirconium hydrochloride (37342-97-5) + 4,4-Bis-diisopropylamino-4λ5-[1,2,3,4]triazaphosphinine-5,6-dicarboxylic acid dimethyl ester (150062-69-4) → C2(OCOCH3)2P(N(C3H7)2)2NHZr(C5H5)2Cl (173104-85-3)

Conditions	Yield
In tetrahydrofuran (Ar); standing (25°C, 20 h); filtn., vac. drying, crystn. (THF, 25°C); elem. anal.;	45%

lithium bis(trimethylsilyl)amide-bis(diethyl ether) complex (78804-38-3) + dicyclopentadienylzirconium hydrochloride (37342-97-5) → Zr(C5H5)2CH2Si(CH3)2NSi(CH3)3 (78804-37-2)

Conditions	Yield
In diethyl ether byproducts: LiN(Si(CH3)3)2*0.5C2H5OC2H5; org. compd. in Et2O added to suspn. of Ti complex in Et2O, mixture stirred at room temp. under Ar for 24 h; filtration, evapn., extn. (pentane), filtration, concg. in vac., cooling (-70°C), concg. of mother liquor, cooling (-70°C), sublimation (70-80°C, 0.001 mm Hg); elem. anal.;	18%