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 00:00:00 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), Vol. 18:11
• Country of Publication: United States
• Language: English

Related Subjects

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