Home
Resources
Publications
P-S Bond Scission by bis(cyclopentadienyl)molybdenum(IV) Dichloride, Cp(2)MoCl(2)(aq): First Documented Example of an Organometallic Complex Hydrolyzing Thiophosphinates

P-S Bond Scission by bis(cyclopentadienyl)molybdenum(IV) Dichloride, Cp(2)MoCl(2)(aq): First Documented Example of an Organometallic Complex Hydrolyzing Thiophosphinates

Louis Y Kuo, Angela P Blum, Michal Sabat

Inorg Chem. 2005 Jul 25;44(15):5537-41.

PMID: 16022553

Abstract:

Thiophosphinate hydrolysis involving P-S bond scission is desirable for the degradation of organophosphate neurotoxins, and we report the first case for such a hydrolytic process by an organometallic compound. The metallocene, bis(cyclopentadienyl)molybdenum(IV) dichloride, Cp(2)MoCl(2) (Cp = eta(5)-C(5)H(5)), hydrolyzes a variety of thioaryl diphenylphosphinates in an aqueous THF solution. P-S scission of p-methoxythiophenyl diphenylphosphinate has a 500-fold rate of acceleration in the presence of Cp(2)MoCl(2)(aq) with activation parameters of 20(3) kcal mol(-)(1) and -15(3) cal mol(-)(1) K(-)(1) for DeltaH(double dagger) and DeltaS(double dagger), respectively. These activation parameters and the rate acceleration are consistent with an intermolecular hydrolytic process in which the Cp(2)Mo serves as a Lewis acid to activate the phosphinate for nucleophilic attack. Furthermore, rho = 2.3 (25 degrees C) which indicates a single nonconcerted mechanism in which the rate determining step is the nucleophilic attack on the activated phosphinate.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP12184224	Bis(cyclopentadienyl)molybdenum(IV) dichloride		12184-22-4	Price

As a specialist in analytical chemical Products, Alfa Chemistry offers consumers a wealth of raw materials and a full range of technologies and services.

QUICK LINKS

HEADQUARTERS

Tel:

Fax:

Email: