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Photochemical Formation of Copper(I) from Copper(II)-Dicarboxylate Complexes: Effects of Outer-Sphere versus Inner-Sphere Coordination and of Quenching by Malonate

Wu, Chien-Hou and Sun, Lizhong and Faust, Bruce C. (2000) Photochemical Formation of Copper(I) from Copper(II)-Dicarboxylate Complexes: Effects of Outer-Sphere versus Inner-Sphere Coordination and of Quenching by Malonate. Journal of Physical Chemistry A, 104 (21). pp. 4989-4996. ISSN 1089-5639. http://resolver.caltech.edu/CaltechAUTHORS:20170719-080938081

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Abstract

Copper(I) quantum yields are reported for Cu(II) complexes of aliphatic dicarboxylates in aqueous solution (N_2-purged), based on steady-state illuminations. For Cu(dicarboxylate)^0, the Cu(I) quantum yields at 313 nm (Φ_(Cu(I),CuL)) exhibit the following trend (25 °C, ionic strength = 0.10 M):  malonate (0.15 ± 0.07) > succinate (0.10 ± 0.02) (Sun, L.; Wu, C.-H.; Faust, B. C. J. Phys. Chem. A 1998, 102, 8664−8672) > glutarate (0.054 ± 0.005) > adipate (0.042 ± 0.004) ≈ pimelate (0.046 ± 0.009). The systematic decrease in Cu(I) quantum yield observed for these Cu(dicarboxylate)^0 complexes parallels the increasing degree of outer-sphere coordination of the complexes. Free uncomplexed malonate species quench the photoformation of Cu(I) from Cu(malonate)^0 in a way that cannot be explained solely based on the Cu(II) speciation. An interpretation based on the quenching of the intermediate [Cu(CH_2C(O)O-)^0] by H(malonate)-/H_2(malonate)^0 is proposed. Evidence is presented for Cu(I) photoformation from Cu(malonate)^0.


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http://dx.doi.org/10.1021/jp992665xDOIArticle
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Additional Information:© 2000 American Chemical Society. Received 29 July 1999. Published online 29 April 2000. Published in print 1 June 2000. We are grateful to Professor Janet G. Hering of the California Institute of Technology for useful discussions and significant assistance with the preparation of this paper. We also thank the reviewers for valuable comments. This study was supported by the U.S. Office of Naval Research, Harbor Processes Program. A portion of this work was presented at the 217th national meeting of the American Chemical Society.
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Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20170719-080938081
Official Citation:Photochemical Formation of Copper(I) from Copper(II)-Dicarboxylate Complexes:  Effects of Outer-Sphere versus Inner-Sphere Coordination and of Quenching by Malonate Chien-Hou Wu, Lizhong Sun, and Bruce C. Faust The Journal of Physical Chemistry A 2000 104 (21), 4989-4996 DOI: 10.1021/jp992665x
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ID Code:79186
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:19 Jul 2017 16:48
Last Modified:19 Jul 2017 16:48

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