Intramolecular Ligand Hydroxylation : Mechanistic Studies on the Reaction of a Copper(I) Schiff Base Complex with Dioxygen - Research portal of Justus Liebig University Giessen:

Journal article

Intramolecular Ligand Hydroxylation : Mechanistic Studies on the Reaction of a Copper(I) Schiff Base Complex with Dioxygen

Authors list: Ryan, S; Adams, H; Fenton, DE; Becker, M; Schindler, S

Publication year: 1998

Pages: 2134-2140

Journal: Inorganic Chemistry

Volume number: 37

Issue number: 9

ISSN: 0020-1669

DOI Link: https://doi.org/10.1021/ic971010c

Publisher: American Chemical Society

Abstract:
The dinuclear copper(I) complex of 1,3-bis[N-(2-pyridylethyl)formimidoyl]benzene, [Cu(2)(H-BPB-H)(CH(3)CN)(2)](BF(4))(2), as well as the 5-nitro derivative, [Cu(2)(NO(2)-BPB-H)(CH(3)CN)(2)](BF(4))(2), react with dioxygen to form phenolate-bridged complexes as products. In a detailed kinetic study activation parameters of DeltaH() = 47 +/- 9 kJ/mol, DeltaS() = -53 +/- 11 J/(mol K), and DeltaV() = -9.5 +/- 0.5 cm(3)/mol for the reaction of [Cu(2)(H-BPB-H)(CH(3)CN)(2)](BF(4))(2) with dioxygen were obtained which account, together with further kinetic findings, for the occurrence of an intermediate peroxo complex that cannot be observed spectroscopically. The crystal structures of the products of the reaction were determined. Crystal data: complex [Cu(2)(H-BPB-O)-OH(H(2)O)](BF(4))(2), formula C(22)H(24)B(2)Cu(2)F(8)N(4)O(3), monoclinic space group P2(1)/c, Z = 4, a = 10.122(2) Å, b = 28.711(6) Å, c = 9.283(2) Å, alpha = 90 degrees, beta = 100.78(3) degrees, and gamma = 90 degrees; complex [Cu(2)(NO(2)-BPB-O)-OH(H(2)O)(3)](BF(4))(2), formula C(22)H(27)B(2)Cu(2)F(8)N(5)O(7), triclinic space group, P&onemacr;, Z = 2, a = 10.144(2) Å, b = 10.7612(2) Å, and c = 16.000(4) Å.

Authors/Editors

- Uni.-Prof. Dr. Siegfried Adolf Schindler

Citation Styles

Harvard Citation style: Ryan, S., Adams, H., Fenton, D., Becker, M. and Schindler, S. (1998) Intramolecular Ligand Hydroxylation : Mechanistic Studies on the Reaction of a Copper(I) Schiff Base Complex with Dioxygen, Inorganic Chemistry, 37(9), pp. 2134-2140. https://doi.org/10.1021/ic971010c

APA Citation style: Ryan, S., Adams, H., Fenton, D., Becker, M., & Schindler, S. (1998). Intramolecular Ligand Hydroxylation : Mechanistic Studies on the Reaction of a Copper(I) Schiff Base Complex with Dioxygen. Inorganic Chemistry. 37(9), 2134-2140. https://doi.org/10.1021/ic971010c