862211-34-5Relevant academic research and scientific papers
P-S bond scission by bis(cyclopentadienyl)molybdenum(IV) dichloride, Cp2MoCl2(aq): First documented example of an organometallic complex hydrolyzing thiophosphinates
Kuo, Louis Y.,Blum, Angela P.,Sabat, Michal
, p. 5537 - 5541 (2005)
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, Cp2MoCl2 (Cp - η5-C5H5), 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 Cp2MoCl2(aq) with activation parameters of 20(3) kcal mol-1 and -15(3) cal mol-1 K-1 for ΔH? and ΔS?, respectively. These activation parameters and the rate acceleration are consistent with an intermolecular hydrolytic process in which the Cp2Mo serves as a Lewis acid to activate the phosphinate for nucleophilic attack. Furthermore, ρ = 2.3 (25°C) which indicates a single nonconcerted mechanism in which the rate determining step is the nucleophilic attack on the activated phosphinate.
