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 Title: GAS-PHASE INFRARED SPECTROSCOPY OF METAL-LIGAND REDOX PAIRS Author(s): Munshi, Musleh Uddin Contributor(s): Oomens, Jos; Martens, Jonathan K.; Berden, Giel Subject(s): Mini-symposium: Far-Infrared Spectroscopy Abstract: Transition metal organometallic complexes are known for their catalytic activation of small molecules. For example, CO$_2$ activation by Ni$^{1+}$(cyclam) complexes has recently been reported in the gas-phase\footnote{F. S. Menges, S. M. Craig, N. T\"otsch, A. Bloomfield, S. Ghosh, H. J. Kr\"uger and M. A. Johnson, {\it Angewandte Chemie International Edition}, 2016, {\bf 55}, 1282-1285.}, where the oxidation state of the metal appeared to be the key for the electrochemical reduction of CO$_2$. In this contribution, we show that metal(II) complexes, including Ni-cyclam, generated via electrospray ionization can be charge reduced inside a quadrupole ion trap mass spectrometer\footnote{J. Martens, G. Berden, C. R. Gebhardt and J. Oomens, {\it Review of Scientific Instruments}, 2016, {\bf 87}, 103108.} (QIT MS) via an electron transfer reduction (ETR) reaction using fluoranthene radical anions as reagents\footnote{M. U. Munshi, S. M. Craig, G. Berden, J. Martens, A. F. DeBlase, D. J. Foreman, S. A. McLuckey, J. Oomens and M. A. Johnson, {\it The Journal of Physical Chemistry Letters}, 2017, {\bf 8}, 5047-5052}. Moreover, their IR spectra can be recorded by action spectroscopy using the FELIX free electron laser, which enables their structural characterization. The complex in either of two charge states is isolated by its {\it m/z}, stored and irradiated with tunable IR light in the range of 500-1800 cm$^{-1}$. IR induced dissociation occurs upon resonant vibrational excitation of the trapped ions, so that an IR spectrum of the (charge reduced) complexes can be obtained by plotting the dissociation yield as a function of IR laser frequency. Experimental spectra are compared with theoretical spectra computed at the density functional theory (DFT) level to obtain detailed structural information of the complexes undergoing charge reduction, eventually providing new insights in their catalytic capabilities. Issue Date: 06/20/18 Publisher: International Symposium on Molecular Spectroscopy Citation Info: APS Genre: Conference Paper / Presentation Type: Text Language: English URI: http://hdl.handle.net/2142/100708 DOI: 10.15278/isms.2018.WI03 Other Identifier(s): WI03 Date Available in IDEALS: 2018-08-172018-12-12
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