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- W2085435146 abstract "Abstract Stopped-flow spectrophotometry was used to study the acid dissociation of the complexes Cu- (daco) 2 2+ and Cu(daco) 2+ (daco = 1,5-diazacyclooctane) with several acids HA at 20 °C and I = 0.1 M (NaClO 4 ). The rate of acid dissociation is independent of [H + ] in the pH range 1.5–6.5 and independent of [HA]. It is base-catalyzed and follows a two-term rate law, rate = ( k o + k A [A − ]) × [Cu- (daco) 2 2+ ] with k o = 0.173 ± 0.003 s −1 and k A = 0 (A − = ClO 4 − , Cl − , I − , NO 3 − , sulfonate), 16.3 ± 1.3 (acetate), 4.6 ± 0.2 (formiate), 3.1 ± 0.3 (chloro- acetate), 1.02 ± 3 (H 2 PO 4 − ), 139 ± 12 (HPO 4 2− ) M −1 s −1 Acid dissociation of the species Cu(daco) 2+ is by a factor of 7 slower than that of the species Cu(daco) 2 2+ . The ratio k o (Cu(daco) 2 2+ ): k o (Ni- (daco) 2 2+ )is 5 × 10 4 :1. There is a LFE relationship between log k A and the p K a of the corresponding acids HA. Ligand replacement in Cu(daco) 2 2+ by EDTA as studied at pH 8 follows the rate law: rate = ( k o + k L [L])[Cu(daco) 2 2+ ] with k o = 0.15 ± 0.01 s −1 and k L = 27.4 ± 0.8 M −1 s − 1 (L ≙ HEDTA 3− ). Rate constant k L also fits reasonably well into the LFE relationship between log k A and p K a . A unifying mechanistic interpretation is presented for both acid dissociation and ligand replacement." @default.
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- W2085435146 date "1990-02-01" @default.
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- W2085435146 title "Kinetic studies on copper(II) complexes with 1,5-diazacyclooctane (= daco): Uncatalyzed and base-catalyzed acid dissociation of Cu(daco)22+ and ligand replacement by EDTA" @default.
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- W2085435146 doi "https://doi.org/10.1016/s0020-1693(00)80940-8" @default.
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