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@ARTICLE{Kick:1052286,
      author       = {Kick, A.-C. and Schatz, Michael and Kahl, C. and Hölscher,
                      M. and Eichel, Rüdiger-A. and Granwehr, Josef and Kaeffer,
                      N. and Leitner, W.},
      title        = {{M}apping proton and carbon dioxide electrocatalytic
                      reductions at a {R}h complex by in situ
                      spectroelectrochemical {NMR}},
      journal      = {Chemical science},
      volume       = {17},
      number       = {3},
      issn         = {2041-6520},
      address      = {Cambridge},
      publisher    = {RSC},
      reportid     = {FZJ-2026-00903},
      pages        = {1637 - 1646},
      year         = {2026},
      abstract     = {Detailed molecular level understanding of organometallic
                      electrocatalytic systems is required to fully exploit their
                      technological potential to store, distribute, and utilise
                      renewable energy in chemical form. However, in situ methods
                      providing high resolution information on the structure and
                      reactivity of transient intermediates remain challenging due
                      to incompatible requirements for standard electrochemical
                      and spectroscopic cell designs. Here, we demonstrate the use
                      of spectroelectrochemical nuclear magnetic resonance
                      (SEC-NMR) to enable operando characterisation of molecular
                      species during organometallic electrocatalysis. The
                      electroreduction of a prototypical molecular rhodium(+I)
                      diphosphine complex was studied under aprotic conditions and
                      in the presence of H2O and/or CO2. By combining multinuclear
                      SEC-NMR, chemical reductions, modelling and simulations, we
                      determine the involved species, their relative
                      concentrations and the competing interconversions. The
                      bielectronic reduction leading to the highly reactive
                      low-valent rhodium(−I) intermediate and subsequent
                      protonation of that species into a Rh–hydride complex was
                      followed in a time-resolved manner. Deuterium labelling and
                      ex situ NMR analysis after SEC-NMR electrolysis revealed
                      that under aprotic conditions the proton source
                      substantially arises from Hofmann elimination of the
                      nBu4NPF6 electrolyte in addition to the acetonitrile
                      solvent. The reactivities of the Rh(−I) and the Rh–H
                      complexes were further monitored under turnover conditions,
                      providing direct molecular insights into bifurcating
                      electrocatalytic pathways for hydrogen evolution and CO2
                      reduction.},
      cin          = {IET-1},
      ddc          = {540},
      cid          = {I:(DE-Juel1)IET-1-20110218},
      pnm          = {1232 - Power-based Fuels and Chemicals (POF4-123) / DFG
                      project G:(GEPRIS)390919832 - EXC 2186: Das Fuel Science
                      Center – Adaptive Umwandlungssysteme für erneuerbare
                      Energie- und Kohlenstoffquellen (390919832)},
      pid          = {G:(DE-HGF)POF4-1232 / G:(GEPRIS)390919832},
      typ          = {PUB:(DE-HGF)16},
      doi          = {10.1039/D5SC05744B},
      url          = {https://juser.fz-juelich.de/record/1052286},
}