Matrix isolation infrared spectroscopic study of the photochemistry of bis(cyclopentadienyl)dicarbonyl titanium in solid nitrogen

Hiroshi Manda, Jun Miyazaki, Yasuhiro Yamada

Research output: Contribution to journalArticle

Abstract

Infrared spectra of the photochemical products of bis(cyclopentadienyl)dicarbonyl titanium, TiCp2(CO)2, isolated in an Ar matrix and a N2 matrix were measured. UV-irradiation of TiCp2(CO)2 produced TiCp2(CO) in the Ar matrix, and three types of nitrogen-containing compounds, TiCp2(CO)(N2), TiCp2(N2), and TiCp2(N2)2 were produced in the N2 matrix. The yields of the species changed with the duration of UV-irradiation. Annealing of the sample resulted in the disappearance of unstable TiCp2(N2) and an increase of TiCp2(N2)2. Isotope shifts of the infrared spectra were measured using 15N2 to confirm the assignments. The structures of the species were estimated using a double hybrid density functional theory calculation (mPW2PLYP/cc-pVTZ), and the calculated infrared frequencies were in very good agreement with the experimentally measured spectra.

Original languageEnglish
Article number127357
JournalJournal of Molecular Structure
Volume1202
DOIs
Publication statusPublished - 15 Feb 2020

Fingerprint

Photochemical reactions
Titanium
Nitrogen
Infrared radiation
Titanium compounds
Irradiation
Isotopes
Density functional theory
Annealing

Keywords

  • Cyclopentadienyl titanium complex
  • Infrared spectroscopy
  • Matrix isolation
  • Nitrogen
  • Photochemistry

Cite this

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title = "Matrix isolation infrared spectroscopic study of the photochemistry of bis(cyclopentadienyl)dicarbonyl titanium in solid nitrogen",
abstract = "Infrared spectra of the photochemical products of bis(cyclopentadienyl)dicarbonyl titanium, TiCp2(CO)2, isolated in an Ar matrix and a N2 matrix were measured. UV-irradiation of TiCp2(CO)2 produced TiCp2(CO) in the Ar matrix, and three types of nitrogen-containing compounds, TiCp2(CO)(N2), TiCp2(N2), and TiCp2(N2)2 were produced in the N2 matrix. The yields of the species changed with the duration of UV-irradiation. Annealing of the sample resulted in the disappearance of unstable TiCp2(N2) and an increase of TiCp2(N2)2. Isotope shifts of the infrared spectra were measured using 15N2 to confirm the assignments. The structures of the species were estimated using a double hybrid density functional theory calculation (mPW2PLYP/cc-pVTZ), and the calculated infrared frequencies were in very good agreement with the experimentally measured spectra.",
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Matrix isolation infrared spectroscopic study of the photochemistry of bis(cyclopentadienyl)dicarbonyl titanium in solid nitrogen. / Manda, Hiroshi; Miyazaki, Jun; Yamada, Yasuhiro.

In: Journal of Molecular Structure, Vol. 1202, 127357, 15.02.2020.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Matrix isolation infrared spectroscopic study of the photochemistry of bis(cyclopentadienyl)dicarbonyl titanium in solid nitrogen

AU - Manda, Hiroshi

AU - Miyazaki, Jun

AU - Yamada, Yasuhiro

PY - 2020/2/15

Y1 - 2020/2/15

N2 - Infrared spectra of the photochemical products of bis(cyclopentadienyl)dicarbonyl titanium, TiCp2(CO)2, isolated in an Ar matrix and a N2 matrix were measured. UV-irradiation of TiCp2(CO)2 produced TiCp2(CO) in the Ar matrix, and three types of nitrogen-containing compounds, TiCp2(CO)(N2), TiCp2(N2), and TiCp2(N2)2 were produced in the N2 matrix. The yields of the species changed with the duration of UV-irradiation. Annealing of the sample resulted in the disappearance of unstable TiCp2(N2) and an increase of TiCp2(N2)2. Isotope shifts of the infrared spectra were measured using 15N2 to confirm the assignments. The structures of the species were estimated using a double hybrid density functional theory calculation (mPW2PLYP/cc-pVTZ), and the calculated infrared frequencies were in very good agreement with the experimentally measured spectra.

AB - Infrared spectra of the photochemical products of bis(cyclopentadienyl)dicarbonyl titanium, TiCp2(CO)2, isolated in an Ar matrix and a N2 matrix were measured. UV-irradiation of TiCp2(CO)2 produced TiCp2(CO) in the Ar matrix, and three types of nitrogen-containing compounds, TiCp2(CO)(N2), TiCp2(N2), and TiCp2(N2)2 were produced in the N2 matrix. The yields of the species changed with the duration of UV-irradiation. Annealing of the sample resulted in the disappearance of unstable TiCp2(N2) and an increase of TiCp2(N2)2. Isotope shifts of the infrared spectra were measured using 15N2 to confirm the assignments. The structures of the species were estimated using a double hybrid density functional theory calculation (mPW2PLYP/cc-pVTZ), and the calculated infrared frequencies were in very good agreement with the experimentally measured spectra.

KW - Cyclopentadienyl titanium complex

KW - Infrared spectroscopy

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