Michael C. Thompson

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

In this work, we investigated how the reductive activation of CO2 with an atomic bismuth model catalyst changes under aprotic solvation. IR photodissociation spectroscopy of mass-selected [Bi(CO2 )n ]- 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 CO2 binds to a bismuth atom in the presence of an excess electron to form a metalloformate ion, BiCOO- . Solvation with additional CO2 molecules leads to the stabilization of a bismuth(I) oxalate complex and results in a core ion switch.

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

We report infrared photodissociation spectra of manganese-CO2 cluster anions, [Mn(CO2)n]- (n = 2-10) to probe structural motifs characterizing the interaction between Mn and CO2 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 CO2 molecules. Structural motifs of ligands evolve with increasing cluster size from simple monodentate and bidentate CO2 ligands to oxalate ligands and combinations of these structural themes.

Structural Motifs of [Fe(CO2)n]− Clusters (n = 3–7)

We present IR spectra and quantum chemical calculations for anionic iron-CO2 clusters of the form [Fe(CO2)n]- (n = 3-7). All observed clusters have at least two CO2 units strongly bound to the metal atom. These strongly bound iron-CO2 complexes form the core ions of the clusters and are solvated by additional, weakly bound CO2 molecules. Larger clusters show clear infrared signatures of core ion isomers with three CO2 moieties as well. Dominant structural motifs are based on bidentate CO2 ligands with Fe-O/Fe-C bonds, oxalate ligands, and metal insertion into a CO bond.

Infrared spectroscopic studies on the cluster size dependence of charge carrier structure in nitrous oxide cluster anions

We report infrared photodissociation spectra of nitrous oxide cluster anions of the form (N2O)(n)O(-) (n = 1-12) and (N2O)n(-) (n = 7-15) in the region 800-1600 cm(-1). The charge carriers in these ions are NNO2(-) and O(-) for (N2O)(n)O(-) clusters with a solvation induced core ion switch, and N2O(-) for (N2O)n(-) clusters. The N-N and N-O stretching vibrations of N2O(-) (solvated by N2O) are reported for the first time, and they are found at (1595 ± 3) cm(-1) and (894 ± 5) cm(-1), respectively. We interpret our infrared spectra by comparison with the existing photoelectron spectroscopy data and with computational data in the framework of density functional theory.

Characterization of Intermediate Oxidation States in CO2 Activation

Redox chemistry during the activation of carbon dioxide involves changing the charge state in a CO2 molecular unit. However, such changes are usually not well described by integer formal charges, and one can think of COO functional units as being in intermediate oxidation states. In this article, we discuss the properties of CO2 and CO2-based functional units in various charge states. Besides covering isolated CO2 and its ions, we describe the CO2-based ionic species formate, oxalate, and carbonate. Finally, we provide an overview of CO2-based functional groups and ligands in clusters and metal-organic complexes.

Heavy atom vibrational modes and low-energy vibrational autodetachment in nitromethane anions

We report infrared spectra of nitromethane anion, CH3NO2 (-), in the region 700-2150 cm(-1), obtained by Ar predissociation spectroscopy and electron detachment spectroscopy. The data are interpreted in the framework of second-order vibrational perturbation theory based on coupled-cluster electronic structure calculations. The modes in the spectroscopic region studied here are mainly based on vibrations involving the heavier atoms; this work complements earlier studies on nitromethane anion that focused on the CH stretching region of the spectrum. Electron detachment begins at photon energies far below the adiabatic electron affinity due to thermal population of excited vibrational states.

Interactions of Molecular Titanium Oxides TiOx (x = 1–3) with Carbon Dioxide in Cluster Anions

We study small titanium oxide-CO2 cluster anions in vacuo to understand the fundamental interactions between TiO x and CO2 in the presence of an excess electron. Infrared spectra of [TiO x(CO2) y]- ( x = 1-3, y > 1) were obtained using photodissociation spectroscopy and assigned through quantum chemistry calculations, identifying the formation of carbonato, oxalato, oxo, η2-(O,O), and carbonyl ligands in the core ions of these clusters, with carbonato ligands being the dominant ligand species.

Infrared Photodissociation Spectra of [Sn(CO2)n]− Cluster Ions

We present infrared spectra and density functional theory calculations of mass selected [Sn(CO2) n]- cluster anions ( n = 2-6). The spectra and structures of these clusters exhibit less structural diversity than those of analogous clusters with first-row transition metals, but are more complex than those for the heavy coinage metals or for the related [Bi(CO2) n]- clusters. The most favorable core ion structure for all cluster sizes can be characterized as a Sn-oxalate complex, Sn[C2O4]-. Higher energy isomers based on a bidentate η2-(C,O) CO2 ligand tightly bound to the metal atom in SnCO2- complexes are also observed, even for the largest cluster sizes studied here. For n = 2, another high energy isomer is found, featuring a CO2 ligand weakly bound to the metal atom in a SnCO2- ion.

Titanium Insertion into CO Bonds in Anionic Ti–CO2 Complexes

We explore the structures of [Ti(CO2) y]- cluster anions using infrared photodissociation spectroscopy and quantum chemistry calculations. The existence of spectral signatures of metal carbonyl CO stretching modes shows that insertion of titanium atoms into C-O bonds represents an important reaction during the formation of these clusters. In addition to carbonyl groups, the infrared spectra show that the titanium center is coordinated to oxalato, carbonato, and oxo ligands, which form along with the metal carbonyls. The presence of a metal oxalato ligand promotes C-O bond insertion in these systems. These results highlight the affinity of titanium for C-O bond insertion processes.