The journal Dalton Transaction features on its front cover the recently published research article “Catalysis of CO2 reduction by diazapyridinophane complexes of Fe, Co, and Ni: CO2 binding triggered by combined frontier MO associations involving a SOMO”, a collaboration between Kyushu University and IQCC.
The previous study on the photochemical CO2 reduction into CO catalyzed by the diazapyridinophane complexes of Fe, Co, and Ni revealed that (i) the Co catalyst shows the highest TOF but degrades rapidly, (ii) the Fe catalyst exhibits a lower TOF relative to Co but shows higher robustness, giving a higher TON, and (iii) the Ni complex shows no activity (Sakaguchi et al., Chem. Commun., 2019, 55, 8552). Here we show our DFT results unveiling that the Fe and Co catalysts can utilize multiple sets of frontier MO associations at the CO2 binding by including one of the SOMOs in a high-spin d7 Fe(I) and d8 Co(I) center, respectively, giving an increased driving force for these oxidative addition steps. Remarkably, two-electron reduction of CO2 to CO2(2-) at the binding step is driven by the two electrons transferred from different d-based orbitals. The CoI species binds CO2 at the rate-limiting step with an activation barrier of 15.0 kcal/mol, rationalizing the high initial TOF observed. However, the CoI(CO) species is given as a dead-end product, consistent with its relatively rapid deactivation. The Fe catalyst possesses a slightly higher barrier in CO2 binding (deltaG‡ = 15.8 kcal/mol) but does not stabilize the FeI(CO) species which readily releases CO (deltaG = 3.5 kcal/mol). The Ni catalyst has the smallest barrier in CO2 binding (deltaG‡ = 11.5 kcal/mol) but the CO release is largely prohibited by the dead-end NiI(CO) species, consistent with its inactive character towards CO2 reduction. The combined results all satisfactorily explain the observed catalytic behaviors.
The corresponding paper was recently published in Dalton Transactions:
Y. Sakaguchi, A. Call, K. Yamauchi, and K. Sakai
“Catalysis of CO2 reduction by diazapyridinophane complexes of Fe, Co, and Ni: CO2 binding triggered by combined frontier MO associations involving a SOMO” Dalton Trans.2021, 50, 15983-15995
Girona, Nov. 29, 2021
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The Institute of Computational Chemistry and Catalysis (IQCC) of the University of Girona (UdG) is a worldwide reference unit in computational chemistry and catalysis that aims at carrying out groundbreaking research on predictive chemistry for catalysis, with special focus on the processes occurring at the confined space for the coming years. [More]