Phosphonothioate Hydrolysis by Molybdocene Dichlorides: Importance of Metal Interaction with the Sulfur of the Thiolate Leaving Group

The metallocene bis(cyclopentadienyl)molybdenum(IV) dichloride Cp2MoCl2 hydrolyzes O,S-diethyl phenylphosphonothioate (1) with only P–S scission to yield a phosphonate under mild aqueous conditions. In terms of degrading phosphonothioate neurotoxins, exclusive cleavage of the P–S linkage is preferre...

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Veröffentlicht in:Organometallics 2013-09, Vol.32 (17), p.4759-4765
Hauptverfasser: Kuo, Louis Y, Baker, Devon C, Dortignacq, Adria K, Dill, Kristina M
Format: Artikel
Sprache:eng
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Zusammenfassung:The metallocene bis(cyclopentadienyl)molybdenum(IV) dichloride Cp2MoCl2 hydrolyzes O,S-diethyl phenylphosphonothioate (1) with only P–S scission to yield a phosphonate under mild aqueous conditions. In terms of degrading phosphonothioate neurotoxins, exclusive cleavage of the P–S linkage is preferred, for P–O scission yields another toxic phosphonothioate. Structure–activity relationship studies were undertaken with various phosphonothioates to test the hypothesis for the exclusive P–S scission by Cp2Mo(aq). Kinetics data show that the rates of phosphonothioate hydrolysis correspond to the size of the alkanethiolate leaving group on treatment with Cp2MoCl2. This suggests that the exclusive P–S scission of 1 is due to the interaction between the thiophilic Cp2Mo with the sulfur site of the P–SR linkage.
ISSN:0276-7333
1520-6041
DOI:10.1021/om400382u