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

Journal Article · · Dalton Transactions
DOI:https://doi.org/10.1039/C4DT03143A· OSTI ID:1221659
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Iowa State Univ., Ames, IA (United States)
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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+.

Research Organization:
Ames Lab., Ames, IA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-07CH11358
OSTI ID:
1221659
Report Number(s):
IS-J-8424; ICHBD9
Journal Information:
Dalton Transactions, Vol. 44, Issue 8; ISSN 1477-9226
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

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Cited By (2)

Mechanistic insights into cobalt( ii / iii )-catalyzed C–H oxidation: a combined theoretical and experimental study journal January 2015
Facile formation of CoN 4 active sites onto a SiO 2 support to achieve robust CO 2 and proton reduction in a noble-metal-free photocatalytic system journal January 2019

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