Photochemical Processes in a Rhenium(I) Tricarbonyl N-Heterocyclic Carbene Complex Studied by Time-Resolved Measurements

Tatsuhiko Mukuta, Peter V. Simpson, Jamila G. Vaughan, Brian W. Skelton, Stefano Stagni, Massimiliano Massi, Kazuhide Koike, Osamu Ishitani, Ken Onda

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

We carried out time-resolved infrared (TR-IR) and emission lifetime measurements on a Re(I) carbonyl complex having an N-heterocyclic carbene ligand, namely, fac-[Re(CO)3(PyImPh)Br], under photochemically reactive (in solution in acetonitrile) and nonreactive (in solution in dichloromethane) conditions to investigate the mechanism of photochemical ligand substitution reactions. The TR-IR measurements revealed that no reaction occurs on a picosecond time scale and the cationic product, namely, fac-[Re(CO)3(PyImPh)(MeCN)]+, is produced on a nanosecond time scale only in solution in acetonitrile, which indicates that the reaction proceeds thermally from the excited state. Because no other products were observed by TR-IR, we concluded that this cationic product is an intermediate species for further reactions. The measurements of the temperature-dependent emission lifetime and analysis using transition-state theory revealed that the photochemical substitution reaction proceeds from a metal-to-ligand charge transfer excited state, the structure of which allows the potential coordination of a solvent molecule. Thus, the coordinating capacity of the solvent determines whether the reaction proceeds or not. This mechanism is different from those of photochemical reactions of other types of Re(I) carbonyl complexes owing to the unique characteristics of the carbene ligand.

Original languageEnglish
Pages (from-to)3404-3413
Number of pages10
JournalInorganic chemistry
Volume56
Issue number6
DOIs
Publication statusPublished - Mar 20 2017

Fingerprint

Rhenium
rhenium
carbenes
Time measurement
time measurement
Ligands
Carbon Monoxide
Infrared radiation
Excited states
ligands
Substitution reactions
acetonitrile
Photochemical reactions
Methylene Chloride
products
substitutes
Charge transfer
life (durability)
Metals
photochemical reactions

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Photochemical Processes in a Rhenium(I) Tricarbonyl N-Heterocyclic Carbene Complex Studied by Time-Resolved Measurements. / Mukuta, Tatsuhiko; Simpson, Peter V.; Vaughan, Jamila G.; Skelton, Brian W.; Stagni, Stefano; Massi, Massimiliano; Koike, Kazuhide; Ishitani, Osamu; Onda, Ken.

In: Inorganic chemistry, Vol. 56, No. 6, 20.03.2017, p. 3404-3413.

Research output: Contribution to journalArticle

Mukuta, T, Simpson, PV, Vaughan, JG, Skelton, BW, Stagni, S, Massi, M, Koike, K, Ishitani, O & Onda, K 2017, 'Photochemical Processes in a Rhenium(I) Tricarbonyl N-Heterocyclic Carbene Complex Studied by Time-Resolved Measurements', Inorganic chemistry, vol. 56, no. 6, pp. 3404-3413. https://doi.org/10.1021/acs.inorgchem.6b02936
Mukuta, Tatsuhiko ; Simpson, Peter V. ; Vaughan, Jamila G. ; Skelton, Brian W. ; Stagni, Stefano ; Massi, Massimiliano ; Koike, Kazuhide ; Ishitani, Osamu ; Onda, Ken. / Photochemical Processes in a Rhenium(I) Tricarbonyl N-Heterocyclic Carbene Complex Studied by Time-Resolved Measurements. In: Inorganic chemistry. 2017 ; Vol. 56, No. 6. pp. 3404-3413.
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