Additions and Corrections 1972, Volume 11 D. Paul Rillema and John F. Endicott: Outer-Sphere Reductions of Cobalt(II1) Complexes Containing Macrocyclic Ligands. A Further Examination of Free Energy Correlations and Anomalous Reorganizational Barriers. Page 2361. In correcting El,,, values we inadvertently added rather than subtracted a calibration correction of 0.08 V, based on Cd(NO,), . In Table IV the correct values are Co(teto)(NH,), (El,, = -0.06 V ; E n = 0.18 V), Co(truns[l4] diene)(”,),,‘ (-0.09; 0.15), Co(DIM)(NH,),’+ (-0.14; 0.10) and Co(TIM)(NH3),’+ (-0.24;
’+
0.00). These changes of potential alter the values of various rate constants computed in Table VI; correct values are indicated in the table below (no correction was required for Co(NH,), 3+ or the transdiaquo complexes). In addition, the last entry in the last column of Table IV should read 1.74”. These corrections do not significantly alter most of the points raised in the Discussion. Two exceptions are in section A the reactivity ranges are about the same for each reducing agent rather than opposite to the Guenther and Linck prediction of a contracted range for Cr*+;and in section C the ki values for aquo and ammine complexes are about the same (within a factor of 10) rather than opposite to a predicted greater reactivity of ammine complexes. &‘-
Comparison of Intrinsic Electron-Transfer Rate Constants (AG,,’= 0) and Apparent Cobalt Self-Exchange Parameters for Reductions of Co(N,)(NH,),” and CO(N,)(OH,)~’ Complexes Reducing agent RU(NH~)~’+
N, teta trans[ 141 diene
VZC
CrZ+
DIM TIM teta trans[ 141 diene DIM TIM teta trans[ 141 diene TIM
k,,, W 1sec-’ ( p = 1.0)
8.4 2.9 6.0 3.7 2.3 2.3 3.1 5.7 3.4 x 10-2 1.5 X lo-* 0.18
(~ll~z*fl,~”z,
KI21’Z 4.7 2.6 1.o 0.14 5.2 x 2.9 x 1.1 x 1.6 X 9.7 x 5.4 x 2.9 X
103 103 103 10’ 104 104 lo4
M-I sec-’ 1.8 1.1 6.1 26 4.4 x 4.8 x 2.8 x 3.6 X 3.5 x 2.8 X 6.2 x
10-4 10-4 10-3 10.’ 10-7 lo-’ 10-5
ki,‘
M-’ sec-‘ 1.8 1.1 6.1 31 7.0 x 7.2 x 4.0 x 4.4 x 5.0 x 7.6 x 1.0 x
10-4 10-4 10-3 10-2 10-7 10-4
log k,b -2.5 -2.9 -1.4 0.0 -3.3 -3.3 -1.8 0.3 -8.6 -6.2 -2
M-’ sec-‘ for self-exchange rates of teta and truns[l4] diene complexes, a ki= k12/K121’2f121’2. In estimatingf,, we have assumed lo-, M-’ sec-’ for DIM complexes, and 1 0 M - ’ sec-’ for TIM complexes. b k , = kiz/kll M-’ sec-’. J . F. EKDICOTT
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