UV-visible spectroscopy of macrocyclic alkyl, nitrosyl and halide complexes of cobalt and rhodium. Experiment and calculation
Abstract
In this paper, transition metal complexes (NH3)5CoX2+ (X = CH3, Cl) and L(H2O)MX2+, where M = Rh or Co, X = CH3, NO, or Cl, and L is a macrocyclic N4 ligand are examined by both experiment and computation to better understand their electronic spectra and associated photochemistry. Specifically, irradiation into weak visible bands of nitrosyl and alkyl complexes (NH3)5CoCH32+ and L(H2O)MIIIX2+ (X = CH3 or NO) leads to photohomolysis that generates the divalent metal complex and ˙CH3 or ˙NO, respectively. On the other hand, when X = halide or NO2, visible light photolysis leads to dissociation of X– and/or cis/trans isomerization. Computations show that visible bands for alkyl and nitrosyl complexes involve transitions from M–X bonding orbitals and/or metal d orbitals to M–X antibonding orbitals. In contrast, complexes with X = Cl or NO2 exhibit only d–d bands in the visible, so that homolytic cleavage of the M–X bond requires UV photolysis. UV-Vis spectra are not significantly dependent on the structure of the equatorial ligands, as shown by similar spectral features for (NH3)5CoCH32+ and L1(H2O)CoCH32+.
- Authors:
-
- Iowa State Univ., Ames, IA (United States)
- Publication Date:
- Research Org.:
- Ames Lab., Ames, IA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1221659
- Report Number(s):
- IS-J-8424
Journal ID: ISSN 1477-9226; ICHBD9
- Grant/Contract Number:
- AC02-07CH11358
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Dalton Transactions
- Additional Journal Information:
- Journal Volume: 44; Journal Issue: 8; Journal ID: ISSN 1477-9226
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Hull, Emily A., West, Aaron C., Pestovsky, Oleg, Kristian, Kathleen E., Ellern, Arkady, Dunne, James F., Carraher, Jack M., Bakac, Andreja, and Windus, Theresa L. UV-visible spectroscopy of macrocyclic alkyl, nitrosyl and halide complexes of cobalt and rhodium. Experiment and calculation. United States: N. p., 2015.
Web. doi:10.1039/C4DT03143A.
Hull, Emily A., West, Aaron C., Pestovsky, Oleg, Kristian, Kathleen E., Ellern, Arkady, Dunne, James F., Carraher, Jack M., Bakac, Andreja, & Windus, Theresa L. UV-visible spectroscopy of macrocyclic alkyl, nitrosyl and halide complexes of cobalt and rhodium. Experiment and calculation. United States. https://doi.org/10.1039/C4DT03143A
Hull, Emily A., West, Aaron C., Pestovsky, Oleg, Kristian, Kathleen E., Ellern, Arkady, Dunne, James F., Carraher, Jack M., Bakac, Andreja, and Windus, Theresa L. Thu .
"UV-visible spectroscopy of macrocyclic alkyl, nitrosyl and halide complexes of cobalt and rhodium. Experiment and calculation". United States. https://doi.org/10.1039/C4DT03143A. https://www.osti.gov/servlets/purl/1221659.
@article{osti_1221659,
title = {UV-visible spectroscopy of macrocyclic alkyl, nitrosyl and halide complexes of cobalt and rhodium. Experiment and calculation},
author = {Hull, Emily A. and West, Aaron C. and Pestovsky, Oleg and Kristian, Kathleen E. and Ellern, Arkady and Dunne, James F. and Carraher, Jack M. and Bakac, Andreja and Windus, Theresa L.},
abstractNote = {In this paper, transition metal complexes (NH3)5CoX2+ (X = CH3, Cl) and L(H2O)MX2+, where M = Rh or Co, X = CH3, NO, or Cl, and L is a macrocyclic N4 ligand are examined by both experiment and computation to better understand their electronic spectra and associated photochemistry. Specifically, irradiation into weak visible bands of nitrosyl and alkyl complexes (NH3)5CoCH32+ and L(H2O)MIIIX2+ (X = CH3 or NO) leads to photohomolysis that generates the divalent metal complex and ˙CH3 or ˙NO, respectively. On the other hand, when X = halide or NO2, visible light photolysis leads to dissociation of X– and/or cis/trans isomerization. Computations show that visible bands for alkyl and nitrosyl complexes involve transitions from M–X bonding orbitals and/or metal d orbitals to M–X antibonding orbitals. In contrast, complexes with X = Cl or NO2 exhibit only d–d bands in the visible, so that homolytic cleavage of the M–X bond requires UV photolysis. UV-Vis spectra are not significantly dependent on the structure of the equatorial ligands, as shown by similar spectral features for (NH3)5CoCH32+ and L1(H2O)CoCH32+.},
doi = {10.1039/C4DT03143A},
journal = {Dalton Transactions},
number = 8,
volume = 44,
place = {United States},
year = {Thu Jan 22 00:00:00 EST 2015},
month = {Thu Jan 22 00:00:00 EST 2015}
}
Web of Science
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