Solvent‐Driven Reductive Activation of CO₂ by Bismuth: Switching from Metalloformate Complexes to Oxalate Products

Abstract

In this work, we investigated how the reductive activation of CO with an atomic bismuth model catalyst changes under aprotic solvation. IR photodissociation spectroscopy of mass-selected [Bi(CO ) ] cluster ions was used to follow the structural evolution of the core ion with increasing cluster size. We interpreted the IR spectra by comparison with density-functional-theory calculations. The results show that CO binds to a bismuth atom in the presence of an excess electron to form a metalloformate ion, BiCOO . Solvation with additional CO molecules leads to the stabilization of a bismuth(I) oxalate complex and results in a core ion switch.

Infrared Spectroscopy of Size‐Selected Hydrated Carbon Dioxide Radical Anions CO2.−(H2O)n (n=2–61) in the C−O Stretch Region

“…formation was found in the reactions with 3‐butyn‐1‐ol as well as with HNO 3. The groups of Weber and Duncan have established a significant amount of data based on the infrared photodissociation spectroscopy of carbon dioxide solvated metal centers M +/− (CO 2 ) n (M=Au, Ag, Co, Ni, Cu, Mg, Fe, Si, V, Al, Bi, TiO), where CO 2 is activated by charge transfer to form the carbon dioxide radical anion CO 2 .− or the oxalate dianion C 2 O 4 2− . Mackenzie et al.…”

Infrared Multiple Photon Dissociation Spectroscopy of Hydrated Cobalt Anions Doped with Carbon Dioxide CoCO2(H2O)n−, n=1–10, in the C−O Stretch Region

“…[29] Cationic metal-CO 2 complexes M + (CO 2 ) n (M = Mg, Al, Si, V, Fe, Co, Ni, Rh, Ir) have been exten-sively investigatedi nt he past decades, [30][31][32][33][34][35][36][37][38][39][40] and also anionic speciesM À (CO 2 ) n (M = Ti,M n, Fe, Co, Ni, Cu, Ag, Au, Sn, Bi) have received considerable attention,f oremost by the group of Weber. [41][42][43][44][45][46][47][48][49][50][51] Generally,t he anionic CO 2 À stretching vibrations shift to the red compared to neutral CO 2 vibrations. [4,52] CO 2 as al igand was also investigated as metal oxides, NbO 2 + (CO 2 ) n and Ta O 2 + (CO 2 ) n by Mackenzie and co-workers.…”

“…Cobalt carbonyl cations Co(CO) n + ( n= 1–9) were investigated in an Ar tagging experiment by the group of Duncan, finding one strong absorption for n= 1 at 2156 cm −1 . Cationic metal–CO 2 complexes M + (CO 2 ) n (M=Mg, Al, Si, V, Fe, Co, Ni, Rh, Ir) have been extensively investigated in the past decades, and also anionic species M − (CO 2 ) n (M=Ti, Mn, Fe, Co, Ni, Cu, Ag, Au, Sn, Bi) have received considerable attention, foremost by the group of Weber . Generally, the anionic CO 2 − stretching vibrations shift to the red compared to neutral CO 2 vibrations .…”

Operation and Performance of a Mass-Selective Cryogenic Linear Ion Trap

“…Another assumption is that the weak binding of the tag only subtly affects the inherent absorption spectrum of the ion. In the 2000’s, it was demonstrated that ions could also be cooled and tagged in cryogenic ion traps [9–11], either with He [12, 13], H 2 [14, 15], D 2 [16, 17], N 2 [18, 19]or Ne [20](so far), and that this approach could then be employed to measure cryogenic IR spectra of ions [12, 18, 20–26]. This major advance in principle allows the coupling of any ionization technique with cryogenic spectroscopic interrogation.…”