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

Abstract

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.

Authors:
Publication Date:
Research Org.:
Univ. of Notre Dame, IN
OSTI Identifier:
5548954
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorg. Chem.; (United States); Journal Volume: 18:11
Country of Publication:
United States
Language:
English
Subject:
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

Citation Formats

Ferraudi, G. Photoinduced redox reactions of macrocyclic complexes with d/sup 7/ (nickel(III)) metal ions. Photoredox processes of equatorial and axial ligands. United States: N. p., 1979. Web. doi:10.1021/ic50201a057.
Ferraudi, G. Photoinduced redox reactions of macrocyclic complexes with d/sup 7/ (nickel(III)) metal ions. Photoredox processes of equatorial and axial ligands. United States. doi:10.1021/ic50201a057.
Ferraudi, G. Thu . "Photoinduced redox reactions of macrocyclic complexes with d/sup 7/ (nickel(III)) metal ions. Photoredox processes of equatorial and axial ligands". United States. doi:10.1021/ic50201a057.
@article{osti_5548954,
title = {Photoinduced redox reactions of macrocyclic complexes with d/sup 7/ (nickel(III)) metal ions. Photoredox processes of equatorial and axial ligands},
author = {Ferraudi, G.},
abstractNote = {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.},
doi = {10.1021/ic50201a057},
journal = {Inorg. Chem.; (United States)},
number = ,
volume = 18:11,
place = {United States},
year = {Thu Nov 01 00:00:00 EST 1979},
month = {Thu Nov 01 00:00:00 EST 1979}
}