Macrocyclic hydroperoxocobalt(III) complex: photochemistry, spectroscopy, and crystal structure

Inorganic Chemistry
Ilia A Guzei, Andreja Bakac

Abstract

The hydroperoxocobalt complex [L(2)(CH(3)CN)CoOOH](ClO(4))(2).CH(3)CN (L(2) = meso-5,7,7,12,14,14-Me(6)-[14]aneN(4)) crystallizes with discrete anions, cations, and solvate acetonitrile molecules in the lattice. The complex crystallizes in the monoclinic space group P2(1)/n, a = 10.4230(5) A, b = 16.1561(8) A, c = 17.4676(9) A, beta = 92.267(1) degrees, V = 2939.2(3) A(3), Z = 4. The O-O bond length is 1.397(4) A, and the O(2)-O(1)-Co angle spans 117.7 degrees. The O-O stretch in the infrared spectrum appears at 815 cm(-1). The 355- and 266-nm photolysis of acidic aqueous solutions of L(2)(H(2)O)CoOOH(2+) results in homolytic splitting of the Co-O bond and yields L(2)Co(H(2)O)(2)(2+) and HO(2)(*)/O(2)(*-) as the only products. The two fragments were scavenged selectively in separate experiments with O(2) and C(NO(2))(4). There is no evidence for photochemical O-O bond homolysis, presumably because the appropriate optical transition is masked by the HO(2)-to-Co LMCT transition.

References

Aug 29, 1995·Proceedings of the National Academy of Sciences of the United States of America·R MacArthurO Einarsdóttir
Oct 24, 2001·Inorganic Chemistry·Gerard RoelfesBen L. Feringa

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Citations

Jun 13, 2006·Chemical Communications : Chem Comm·Peter CombaHubert Wadepohl
Feb 24, 2015·Journal of the American Chemical Society·Sunghee KimKenneth D Karlin
Sep 22, 2011·Journal of the American Chemical Society·Thomas S Teets, Daniel G Nocera
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Dec 10, 2016·Inorganic Chemistry·Bongki ShinJaeheung Cho
Jul 2, 2019·Journal of the American Chemical Society·Ashley M WrightKaren I Goldberg

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