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Title:AN INFRARED PHOTODISSOCIATION SPECTROSCOPIC AND THEORETICAL STUDY OF M(CO)6,7,8+ (M = Ti, Zr, Hf)
Author(s):Lei, Shujun
Contributor(s):Zhou, Mingfei ; Jin, Jiaye
Subject(s):Fundamental interest
Abstract:Spectroscopic and theoretical study of extreme coordinated metal carbonyl complexes has been a subject of intensive studies.\footnote{Zhou, M. F.; Frenking, G. Angew. Chem. Int. Ed. 2018, 57(21), 6236-6241; Science, 2018, 361(6405), 912-916.} M(CO)$_{n}^{+}$ (M = Ti, Zr, Hf) ions were produced by ablating a metal target in a pulse of CO seeded helium, and further studied by mass-selected infrared photodissociation spectroscopy in the carbonyl stretching region. Ti(CO)$_{6}^{+}$ is formed as dominant species in the mass spectrum, while M(CO)$_{6,7,8}^{+}$ ions are of the most abundant species in the mass spectra for zirconium and hafnium. The infrared spectra of M(CO)$_{6}^{+}$ (M = Ti, Zr, Hf) show good agreement with previous reports.\footnote{Duncan, M. A. J. Phys. Chem. A, 2013, 117(46), 11695–11703.} M(CO)$_{7}^{+}$ (M = Zr, Hf) ions only dissociate under focused laser irradiation and have one broad band, indicating strongly coordinated complexes. M(CO)$_{8}^{+}$ (M = Zr, Hf) complexes can fragment by one CO molecule in unfocused light, and each exhibits an infrared band centered at 2084 \wn (Zr) and 2072 \wn (Hf). Theoretical calculations indicate that the M(CO)$_{7}^{+}$ (M = Zr, Hf) complexes are at doublet ground states with \textit{C}$_{2v}$ symmetry. The M(CO)$_{8}^{+}$ (M = Zr, Hf) complexes are identified as 19-electron octacarbonyls. Each of them has \textit{D}$_{4}$ symmetry (distorted cubic geometry) and a doublet ground state. The results extend the knowledge of extreme coordinated carbonyl complexes to Group 4 metals, and provide insights into the ion growth mechanisms in the gas phase.
Issue Date:2019-06-18
Publisher:International Symposium on Molecular Spectroscopy
Genre:Conference Paper / Presentation
Type:Text
Language:English
URI:http://hdl.handle.net/2142/104318
DOI:10.15278/isms.2019.TE05
Rights Information:Copyright 2019 Shujun Lei
Date Available in IDEALS:2019-07-15
2020-01-25


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