Accessing Metal-Specific Orbital Interactions in C-H Activation using Resonant Inelastic X-ray Scattering

26 July 2023, Version 1


Photochemically prepared transition-metal complexes are known to be effective at cleaving the strong C-H bonds of organic molecules in room temperature solutions. There is also ample theoretical evidence that the bidirectional charge-transfer between an incoming alkane C-H group and the transition metal is the decisive interaction in the C-H activation reaction. What is missing, however, are experimental methods to directly probe these interactions in order to reveal what determines reactivity of intermediates and the rate of the reaction. Here, we propose metal specific and time-resolved valence-to-core resonant inelastic X-ray scattering (VtC-RIXS) at the transition metal L-edge as a method to provide a full account of the evolution of metal-alkane interactions during transition-metal mediated C-H activation reactions. For the model system cyclopentadienyl rhodium dicarbonyl (CpRh(CO)2), we demonstrate with a combination of experiment and quantum chemical simulation how the Rh-centered valence-excited final states probed with VtC-RIXS directly reflect changes in donation and back-donation between the alkane C-H group and the transition metal as the reaction proceeds via its intermediates. Following the initial photo-triggered CO dissociation, we find substantial reduction in charge donation onto the metal and the resulting stabilization of metal-centered states as the alkane coordinates to the Rh center in a σ-complex intermediate. C-H bond cleavage in the final oxidative addition step is instead characterized by a substantial increase in back-donation as the new Rh-hydrogen and Rh-carbon bonds are formed. We benchmark and validate our simulations against experimental steady-state measurements. With our study, we predict the key spectral fingerprints for future time-resolved experiments of C-H activation reactions with CpRh(CO)2 and related compounds.


C-H activation
X-ray spectroscopy
organometallic chemistry
frontier molecular orbital interactions

Supplementary materials

Supporting Information for Accessing Metal-Specific Orbital Interactions in C-H Activation using Resonant Inelastic X-ray Scattering
Contains Supporting Figures of molecular orbitals, Experimental and simulated RIXS spectra of Rh(acac)CO2, RIXS spectra at the RASPT2 level of theory


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