The hydrolytic efficiency of the hydrophilic Cu(II) complex of tetrame
thylethylenediamine (TMED C-1 . Cu(II)) and the amphiphilic N-n-hexade
cyl-N,N',N'-trimethylethylenediamine complex (TMED C-16. Cu(II)) in co
micelles with CTANO(3) was studied toward a series of phosphate triest
ers and diesters that were either neutral (1-7) or cationic and amphip
hilic (8-10). While the pseudo-first-order rate constants at [catalyst
] = 1 x 10(-3) M are larger (ca. one order of magnitude) for the micel
lar catalyst, the second-order rate constants are higher for the hydro
philic catalyst. With phosphate triesters, regardless of the structure
of the substrate, TMED C1(.) Cu(II)-bound OH- is a better nucleophile
than free OH-, while TMED C-16. Cu(II)-bound OH- is poorer. This is e
xplained by electrophilic assistance of the metal center which greatly
diminishes in micelles. With phosphate diesters the OH- bound to both
TMED C-1 . Cu(II) and TMED C-16. Cu(II) is a better nucleophile than
free OH-. Partial neutralization of the negative charge of the substra
te may explain this behavior. In all cases the amphiphilic substrates
are intrinsically more reactive than the neutral ones. Comparison with
an iodosobenzoate-based catalyst shows that this is ineffective with
phosphate diesters while it is a better reagent than the metallomicell
ar one with phosphate triesters. Its higher effectiveness, however, se
ems to vanish as the substrate becomes less reactive.