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Title: UV-visible spectroscopy of macrocyclic alkyl, nitrosyl and halide complexes of cobalt and rhodium. Experiment and calculation

Abstract

In this paper, transition metal complexes (NH 3) 5CoX2 + (X = CH 3, Cl) and L(H 2O)MX 2+, where M = Rh or Co, X = CH 3, NO, or Cl, and L is a macrocyclic N 4 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 (NH 3) 5CoCH 3 2+ and L(H 2O)M IIIX 2+ (X = CH 3 or NO) leads to photohomolysis that generates the divalent metal complex and ˙CH3 or ˙NO, respectively. On the other hand, when X = halide or NO 2, 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 NO 2 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 (NH 3) 5CoCH 3 2+ and L 1(Hmore » 2O)CoCH 3 2+.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Laboratory (AMES), 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:
Journal Article: 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. 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, and Windus, Theresa L.. Thu . "UV-visible spectroscopy of macrocyclic alkyl, nitrosyl and halide complexes of cobalt and rhodium. Experiment and calculation". United States. doi: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}
}

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