Polynuclear complexes containing the redox noninnocent Schiff base ligand 2-[(E)-2-mercaptophenylimino]methyl-4,6-di-tert-butylphenolate(2-)

Roy, N., Sproules, S. , Bothe, E., Weyhermüller, T. and Wieghardt, K. (2009) Polynuclear complexes containing the redox noninnocent Schiff base ligand 2-[(E)-2-mercaptophenylimino]methyl-4,6-di-tert-butylphenolate(2-). European Journal of Inorganic Chemistry, 2009(18), pp. 2655-2663. (doi: 10.1002/ejic.200900168)

Abstract

The N,O,S-donor Schiff base ligand 2-[(E)-(2-mercaptophenylimino)methyl]-4,6-di-tert-butylphenolate(2–) (H2L) was deprotonated with triethylamine (2 equiv.) and treated with equimolar amounts of Cu(OAc)2·H2O, PtCl2, Pd(OAc)2, and CoCl2, respectively. The versatility of L2– is realized in the self-assembly of four polynuclear complexes: dimeric [CuII2(L)2] (1), trimeric [PtII3(L)3] (2), and the two tetrameric complexes [PdII4(L)4] (3) and [CoIII4(L)6] (4), all characterized by X-ray crystallography. Electronic structure calculations (DFT) on dimeric 1 show that the two singly occupied Cudmath image orbitals are antiferromagnetically coupled, and the calculated J = –724 cm–1 agrees well with the experimental data. Complexes 3 and 4 possess several reversible one-electron, ligand-centered oxidations with electronic absorption and EPR spectroscopy displaying all the hallmarks of coordinated phenoxyl radicals. This feature further endorses our assignment of the generation of phenoxyl radicals upon oxidation and underscores the redox noninnocence of this Schiff base ligand.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Sproules, Dr Stephen
• Authors: Roy, N., Sproules, S., Bothe, E., Weyhermüller, T., and Wieghardt, K.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: European Journal of Inorganic Chemistry
• Journal Abbr.: Euro. J. Inorg. Chem
• Publisher: Wiley-VCH Verlag
• ISSN: 1434-1948
• ISSN (Online): 1099-0682