Berichtigung: Mediated Inner-Sphere Electron Transfer Induces Homogeneous Reduction of CO2 via Through-Space Electronic Conjugation
It has come to the authors attention that the experimental turnover frequencies (TOFs) were calculated incorrectly by using a second-order rate constant for the reaction instead of the first-order observed rate constant as defined in the original derivation.1, 2 The presented TOF values from re-analyzed experimental electrolysis data are shown below in an updated version of Table 1. These values should replace those in the originally published Table 1 and also replace their mention and discussion in the originally published Abstract and text.
Conditions |
Potential (V vs. Fc+/Fc) |
FECO [%] |
TOFCPE [s–1] |
η [V] |
TONCO (w.r.t [1]) |
TONCO (w.r.t [DBTD]) |
|---|---|---|---|---|---|---|
[Cr] |
−2.3 |
0 |
– |
– |
– |
– |
DBTD |
−2.3 |
32±1 |
– |
– |
– |
0.90 |
[Cr]+DBTD |
−2.3 |
91±10 |
36.8 |
0.69 |
16 |
3.1 |
DBTD+PhOH |
−2.3 |
28±1 |
– |
– |
– |
0.52 |
[Cr] + PhOH |
−2.3 |
111±14 |
7.12 |
0.11 |
11.4 |
– |
[Cr]+ PhOH+DBTD |
−2.3 |
102±14 |
65.3 |
0.41 |
29 |
5.8 |
[Cr] |
−2.7 |
57±3 |
– |
1.14 |
0.81 |
– |
[Cr]+PhOH[a] |
−2.1 |
96±8 |
4.35 |
0.11 |
15[a] |
– |
- * –[Cr]=Cr(tbudhbpy)Cl(H2O) 1. PhOH=0.6 M [PhOH]. Turnovers correspond to moles of electrons passed in coulometry studies divided by two to account for CO formation. [a] Previously reported results.3
These corrections do not affect the primary conclusions and mechanistic analysis presented in the published Communication. However, any discussion of the experimental TOF values in comparison to other previously reported systems no longer applies. Consistent with this, the revised Supporting Information document now shows the correct derivation of TOFs from electrolysis data, as well as a revised catalytic Tafel Plot in Figure S35.
