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Title: Breaking Scaling Relationships in CO2 Electroreduction with Isoelectronic Analogs [Fe4N(CO)12]– and [Fe3MnO(CO)12]–

Journal Article · · Organometallics
 [1];  [1]; ORCiD logo [1]
  1. Univ. of California, Davis, CA (United States)
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[Fe4N(CO)12]-0 and [Fe3MnO(CO)12]- have the same total electron count and overall charge, as well as similar reduction potentials of -1.21 and -1.17 V vs SCE in MeCN, respectively. Both clusters form the reduced hydride upon single electron transfer (ET) and proton transfer (PT). It is known that [Fe4N(CO)12]- is an electrocatalyst for selective CO2 reduction to formate at -1.2 V vs SCE in either pH 7 buffered water or in MeCN/H2O (95:5) and an effective electrocatalyst for H+ reduction to H2 under N2 under the same conditions. In contrast, [Fe3MnO(CO)12]=- affords no products upon electrolysis, beyond [H-Fe3MnO(CO)12]-. We determine that [H-Fe3MnO(CO)12]- is a weaker hydride donor than [H-Fe4N(CO)12]- by about 4 kcal mol–1, and this is a breaking of the hydricity versus reduction potential scaling relationship previously established for a series of metal carbonyl clusters electrocatalysts.

Research Organization:
Univ. of California, Davis, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0016395
OSTI ID:
1657669
Alternate ID(s):
OSTI ID: 1773842
Journal Information:
Organometallics, Vol. 39, Issue 9; ISSN 0276-7333
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

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