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Solvent effects on reactions of hydroxide ion with phosphorus(V) esters. A quantitative treatment
Author(s) -
Bunton Clifford A.,
Gillitt Nicholas D.,
Kumar Anurag
Publication year - 1996
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/(sici)1099-1395(199603)9:3<145::aid-poc763>3.0.co;2-e
Subject(s) - chemistry , phosphinate , hydroxide , solvent , phosphate , inorganic chemistry , reaction rate constant , transition state , ion , solvent effects , trimethyl phosphate , organic chemistry , kinetics , catalysis , fire retardant , physics , quantum mechanics
Second‐order rate constants of reactions of HO − with phosphate, phosphinate and thiophosphinate esters, (PhO) 2 PO.OC 6 H 4 NO 2 ‐ p , Ph 2 PO.OC 6 H 4 NO 2 ‐ p , Ph 2 PO.SPh, Ph 2 PO.SC 6 H 4 NO 2 ‐ p and Ph 2 PO.SEt, go through minima with decreasing water content of H 2 O‐MeCN or H 2 O‐ t ‐BuOH. The rate decrease is due to stabilization of the non‐ionic ester on addition of organic solvent to H 2 O. This inhibition is partially offset by stabilization of the anionic transition states and in the drier solvents partial desolvation of HO − increases rates.