Author: Hay Robert Govan Norman Norman Paul
Publisher: Springer Publishing Company
ISSN: 0340-4285
Source: Transition Metal Chemistry, Vol.23, Iss.2, 1998-04, pp. : 133-138
Disclaimer: Any content in publications that violate the sovereignty, the constitution or regulations of the PRC is not accepted or approved by CNPIEC.
Abstract
The base hydrolysis and spontaneous water hydrolysis of the phosphonate ester 2,4-dinitrophenyl ethyl methylphosphonate (DNPEMP) has been studied in detail and the activation parameters for these processes determined. The catalytic effect of a series of 19 oxygen and nitrogen bases and metal hydroxo complexes has been studied. The Brønsted plot of pK versus logkN has a slope () of 0.47, which is fairly typical for phosphate and phosphonate esters. alpha-Effect nucleophiles such as 2-iodosobenzoate, hypochlorite and the hydroperoxide ion (HO-2) exhibit enhanced reactivity, as does fluoride ion and the bifunctional metal complex [Cu(tmen) (OH2)(OH)]+ (tmen = N,N,N',N',-tetramethylethylenediamine). Reactions involving these species appear to take place by a nucleophilic pathway, while the other oxygen and nitrogen bases act as general base catalysts. The solvent deuterium isotope effect for Et3N catalysis, kH2O/kD2O=1.3, is consistent with general base catalysis. The mechanisms of these reactions are discussed in detail.
Related content
By Sai Chodavarapu Hela Pamidipati Sridhar Yeleswarapu Anipindi Nageswara
Transition Metal Chemistry, Vol. 23, Iss. 3, 1998-06 ,pp. :
By Xu Fei Shi Xiangli Li Yunfeng Zhang Qingzhu
International Journal of Molecular Sciences, Vol. 16, Iss. 9, 2015-08 ,pp. :