An infrared photodissociation spectroscopic and theoretical study of M(CO)6,7,8+ (M = Ti, Zr, Hf)

Lei, Shujun

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https://hdl.handle.net/2142/104318 Copy

Description

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

Issue Date

2019-06-18

Keyword(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.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

eng

Permalink

http://hdl.handle.net/2142/104318

DOI

https://doi.org/10.15278/isms.2019.TE05

Copyright and License Information

Copyright 2019 Shujun Lei

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