Leah G. Dodson, Michael C. Thompson, J. Mathias Weber Infrared photodissociation cluster studies on CO2 interaction with titanium oxide catalyst models Leah G. Dodson, Michael C. Thompson, J. Mathias Weber JILA, NIST, and Department of Chemistry and Biochemistry University of Colorado, Boulder, Colorado 72nd International Symposium on Molecular Spectroscopy June 21, 2017 WD10

TiO2 Surface Modification by CO2 carboxylic acid anchors on TiOx introduction of band-tail states by bidentate CO2 ligands Zhang and Cole, ACS Appl. Mater. Interfaces 2015, 7,3427. Ma et al., Cat. Comm. 2017, 95, 1.

Metal-CO2 Anionic Cluster Binding Motifs Co, Ni, Cu, Mn, Fe Bi, Mn, Fe Mn, Fe Au, Ag, Cu, Bi Co, Ni, Fe Fe Knurr and Weber, J. Am. Chem. Soc. 2012, 134, 18804. Knurr and Weber, J. Phys. Chem. A 2013, 117, 10764. Knurr and Weber, J. Phys. Chem. A 2014, 118, 4056. Knurr and Weber, J. Phys. Chem. A 2014, 118, 8753. Miller et al., Angew. Chem. Int. Ed. 2014, 53, 14407. Thompson et al., Angew. Chem. Int. Ed. 2016, 55, 15171. Thompson et al., J. Phys. Chem. A 2017, 121, 4132. *Titanium: Oxophilic, Small

Ligand Formation in [TiOx(CO2)y]− Clusters Titanium: good at stabilizing highly unstable ligands (carbonate, oxalate). Highly oxophilic: metal-oxygen bond formation. Carbonate Ligand Ti, TiO, TiO2, TiO3 η2-(O,O) Carbene Ligand TiO, TiO2 η2-(C,O) Bidentate Ligand TiO2 Oxalate Ligand Ti, TiO Carbonyl Ligand (Insertion Structures) carbonate η2-(O,O) carbene η2-(C,O) bidentate oxalate carbonyl

Infrared Photodissociation Spectroscopy Mass Selection Photodissociation Reflectron TOF 950–2400 cm−1 [TiOx∙(CO2)y]− Laser ablation CO2 expansion Ti CO2 [TiO2∙(CO2)3]− + hν [TiO2∙(CO2)3]− [TiO2∙(CO2)3]− + hν  [TiO2∙(CO2)2]− + CO2

Data unpublished at time of archiving Data unpublished at time of archiving. They may be restored to this file after publication.

Summary Titanium stabilizes diverse ligand structures Carbonate ligands present in all TiOx (x = 0–3) Bidentate CO2 ligands (η2-(C,O) and η2-(O,O)) High degrees of coordination

Research Associateship Acknowledgements NSF AMO PFC NIST NRC Research Associateship