1984
DOI: 10.1021/ja00330a064
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Electrochemical reduction of carbon dioxide catalyzed by Rh(diphos)2Cl

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Cited by 137 publications
(66 citation statements)
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“…The cyclic voltammograms (CVs) of complexes 1−5 show single reversible 2-electron reductions ( Figure 3) corresponding to the d 8 /d 10 couple, which are consistent with the electrochemistry of previously reported Rh(I) bis-diphosphine complexes. 15,22 The observed reductions are diffusion controlled, as indicated by linear plots of the peak current against the square root of the scan rate. The 2-electron nature of this couple is evident in the splitting of the cathodic and anodic peaks, which fall between the 60 mV expected for a completely reversible one-electron reduction and the 30 mV expected for a completely reversible 2-electron reduction (Table 3).…”
Section: ■ Results and Discussionmentioning
confidence: 93%
“…The cyclic voltammograms (CVs) of complexes 1−5 show single reversible 2-electron reductions ( Figure 3) corresponding to the d 8 /d 10 couple, which are consistent with the electrochemistry of previously reported Rh(I) bis-diphosphine complexes. 15,22 The observed reductions are diffusion controlled, as indicated by linear plots of the peak current against the square root of the scan rate. The 2-electron nature of this couple is evident in the splitting of the cathodic and anodic peaks, which fall between the 60 mV expected for a completely reversible one-electron reduction and the 30 mV expected for a completely reversible 2-electron reduction (Table 3).…”
Section: ■ Results and Discussionmentioning
confidence: 93%
“…Previous reports have suggested that the oxygen from CO 2 is transferred to an unknown oxide acceptor (19). The oxide acceptor can be a proton that can be extracted from acetonitrile (20) or even from the supporting electrolyte via Hoffman degradation (21). More recently, evidence pointing to protons as the oxide acceptor was reported by Wong et al They showed that the catalytic current increased for the reduction of ReðbipyÞðCOÞ 3 ðpyÞðOTfÞ under CO 2 in the presence of increasing concentrations of weak Brönsted acids (22).…”
Section: Uv-vis Stopped-flow Spectroscopy: Probing the Selectivity Ofmentioning
confidence: 99%
“…9,23,24 Mechanistic insights have been gained recently too with Re, [28][29][30] Mn 31,32 and Ni 33-36 based catalysts through electrochemical and spectroscopic analysis, and quantum chemistry calculations. The reduction of carbon dioxide into formate has been more rarely observed using molecular catalysts, in electrochemical conditions with Fe, Ni, Co, Ru, Rh or Ir based catalysts [37][38][39][40][41][42][43][44][45][46][47][48][49] (see also tables 2 and 3 in reference 7) and in photochemical conditions 13,14,[50][51][52][53] with Re, Ru, Ir main-2 ly and very recently Mn complexes. 53 Mechanistic studies have accordingly been scarce.…”
mentioning
confidence: 99%