Photoinduced redox reactions of macrocyclic complexes with d/sup 7/ (nickel(III)) metal ions. Photoredox processes of equatorial and axial ligands

Journal Article · Thu Nov 01 04:00:00 EST 1979 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic50201a057· OSTI ID:5548954

Ferraudi, G

Ultraviolet irradiations of Ni((14)dieneN/sub 4/)(CH/sub 3/CN)/sub 2//sup 3 +/ or Ni(tet a)(CH/sub 3/CN)/sub 2//sup 3 +/ induce a reduction of the metal center and oxidation of the coordinated acetonitrile. The photoprocesses of the tet a and (14)dieneN/sub 4/ complexes have the same threshold energy for photoreactivity, E/sub th/ approx. = 79.4 kcal/mol. However, the limiting yield for Ni(tet a)(CH/sub 3/CN)/sub 2//sup 3 +/, phi = 0.03, is smaller than the yield for Ni((14)dieneN/sub 4/)(CH/sub 3/CN)/sub 2//sup 3 +/, phi = 0.15. The photooxidation of the imino groups of the macrocycle has been observed in flash photolyses of Ni((14)dieneN/sub 4/)(CH/sub 3/CN)/sub 2//sup 3 +/ in the presence of sulfate ions. A Ni(II)-ligand radical (lambda/sub max/ approx. 535 nm, t/sub 1/2/ less than or equal to 600 ..mu..s) was detected in these irradiations. The photochemistries of the Ni(III) complexes have been associated with the population of charge-transfer ligand to metal states, CT/sub ..pi..-C==N ..-->.. d-Ni/ and/or CT/sub ..pi..-imino ..-->.. d-Ni/. 4 figures, 1 table.

• Research Organization: Univ. of Notre Dame, IN
• OSTI ID: 5548954
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 18:11; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
DATA FORMS
DECOMPOSITION
ELECTROMAGNETIC RADIATION
EXPERIMENTAL DATA
GRAPHS
INFORMATION
LIGANDS
NICKEL COMPLEXES
NICKEL COMPOUNDS
NUMERICAL DATA
OXIDATION
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOLYSIS
RADIATIONS
REDOX REACTIONS
SULFATES
SULFUR COMPOUNDS
TABLES
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
ULTRAVIOLET RADIATION