Interaction of CO₂ with Atomic Manganese in the Presence of an Excess Negative Charge Probed by Infrared Spectroscopy of [Mn(CO₂)_n]⁻ Clusters

Abstract

We report infrared photodissociation spectra of manganese-CO cluster anions, [Mn(CO)] (n = 2-10) to probe structural motifs characterizing the interaction between Mn and CO in the presence of an excess electron. We interpret the experimental spectra through comparison with infrared spectra predicted from density functional theory calculations. The cluster anions consist of core ions combining a Mn atom with a variety of ligands, solvated by additional CO molecules. Structural motifs of ligands evolve with increasing cluster size from simple monodentate and bidentate CO ligands to oxalate ligands and combinations of these structural themes.

Infrared Study of OCS Binding and Size-Selective Reactivity with Gold Clusters, Aun+ (n = 1–10)

“…LUMO orbital, which drives bending of the molecule. [95][96][97] Although most common in anionic species, 103,[124][125][126] Jiang and coworkers, and others have observed cationic clusters donating electron density for CO2 activation, 127 128 and Fielicke et al described the ability of Aun + to activate NO molecules. 7 Hence, even though positively charged, the unpaired electron in the even n clusters is diffuse, weakly-bound, and readily donated (see Figure 11c).…”

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 .…”

Theoretical investigations of spin‐orbit coupling and intersystem crossing in reaction carbon dioxide activated by [Re(CO)2]+

“…Futher, activation of CO 2 by a metal hydride ion [LTiH] + (L = Cp2, O), PtH n − , FeH − . In addition, M + (CO2) n (M = Co, Rh, Ir; n = 2‐15) and M − (CO2) n complexes (M = Au, Ag, Co, Mn, Cu, Fe, and Ni) ion‐molecule complexes are coordinated with carbon dioxide, this is also a current research hotspot. However, these reactions are mainly experimental and there is no detailed explanation of the reaction mechanism.…”