Ancillary Ligand Effects upon the Photochemistry of Mn(bpy)(CO)3X Complexes (X = Br-, PhCC-)

Veeranna Yempally, Salvador Moncho Escriva, Faraj Hasanayn, Wai Yip Fan, Edward Brothers, Ashfaq A. Bengali

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Abstract

The photochemistry of two Mn(bpy)(CO)3X complexes (X = PhCC-, Br-) has been studied in the coordinating solvents THF (terahydrofuran) and MeCN (acetonitrile) employing time-resolved infrared spectroscopy. The two complexes are found to exhibit strikingly different photoreactivities and solvent dependencies. In MeCN, photolysis of 1-(CO)(Br) [1 = Mn(bpy)(CO)2] affords the ionic complex [1-(MeCN)2]Br as a final product. In contrast, photolysis of 1-(CO)(CCPh) in MeCN results in facial to meridional isomerization of the parent complex. When THF is used as solvent, photolysis results in facial to meridional isomerization in both complexes, though the isomerization rate is larger for X = Br-. Pronounced differences are also observed in the photosubstitution chemistry of the two complexes where both the rate of MeCN exchange from 1-(MeCN)(X) by THFA (tetrahydrofurfurylamine) and the nature of the intermediates generated in the reaction are dependent upon X. DFT calculations are used to support analysis of some of the experiments.

Original languageEnglish
Pages (from-to)11244-11253
Number of pages10
JournalInorganic Chemistry
Volume56
Issue number18
DOIs
Publication statusPublished - 18 Sep 2017

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Photochemistry
Photochemical reactions
Carbon Monoxide
photochemical reactions
isomerization
photolysis
Photolysis
Isomerization
Ligands
ligands
Photoreactivity
acetonitrile
infrared spectroscopy
Discrete Fourier transforms
chemistry
Infrared spectroscopy
Spectrum Analysis
products
Experiments

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Ancillary Ligand Effects upon the Photochemistry of Mn(bpy)(CO)3X Complexes (X = Br-, PhCC-). / Yempally, Veeranna; Moncho Escriva, Salvador; Hasanayn, Faraj; Fan, Wai Yip; Brothers, Edward; Bengali, Ashfaq A.

In: Inorganic Chemistry, Vol. 56, No. 18, 18.09.2017, p. 11244-11253.

Research output: Contribution to journalArticle

Yempally, Veeranna ; Moncho Escriva, Salvador ; Hasanayn, Faraj ; Fan, Wai Yip ; Brothers, Edward ; Bengali, Ashfaq A. / Ancillary Ligand Effects upon the Photochemistry of Mn(bpy)(CO)3X Complexes (X = Br-, PhCC-). In: Inorganic Chemistry. 2017 ; Vol. 56, No. 18. pp. 11244-11253.
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AB - The photochemistry of two Mn(bpy)(CO)3X complexes (X = PhCC-, Br-) has been studied in the coordinating solvents THF (terahydrofuran) and MeCN (acetonitrile) employing time-resolved infrared spectroscopy. The two complexes are found to exhibit strikingly different photoreactivities and solvent dependencies. In MeCN, photolysis of 1-(CO)(Br) [1 = Mn(bpy)(CO)2] affords the ionic complex [1-(MeCN)2]Br as a final product. In contrast, photolysis of 1-(CO)(CCPh) in MeCN results in facial to meridional isomerization of the parent complex. When THF is used as solvent, photolysis results in facial to meridional isomerization in both complexes, though the isomerization rate is larger for X = Br-. Pronounced differences are also observed in the photosubstitution chemistry of the two complexes where both the rate of MeCN exchange from 1-(MeCN)(X) by THFA (tetrahydrofurfurylamine) and the nature of the intermediates generated in the reaction are dependent upon X. DFT calculations are used to support analysis of some of the experiments.

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