Activation barriers in the .alpha.-cleavage processes of acetaldehyde

3.3 X 104 M'1 s'1 (in their notation, k43k35/k34 for the first .... 0022-3654/87/2091-5111S01.50/0 the barriers arise from ... high energy barrierof 6...
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J . Phys. Chem. 1987, 91, 51 11-51 12

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whether the preequilibration proceeds predominantly via Ni L H F= Ni-LH or via L H F= L 2 Ni-L Ni-LH. Consequently, the authors cannot differentiate between the two limiting cases which they consider. In the end both limiting cases lead to a rate constant for the reaction of Ni2+ with L2- (of DNSA) of k = 3.3 X lo4 M-' s-l (in their notation, k43k35/k34 for the first limiting case and k4, for the second limiting case). This value agrees very well with ours, k l = 3.1 X lo4 M-I s-I for DNSA. For the reaction with HL- results from their evaluation (both This value, too, is consistent limiting cases) k