Strategic synthesis of [Cu2], [Cu4] and [Cu5] complexes: inhibition and triggering of ligand arm hydrolysis and self-aggregation by chosen ancillary bridges

Das, M., Canaj, A. B. , Bertolasi, V., Murrie, M. and Ray, D. (2018) Strategic synthesis of [Cu2], [Cu4] and [Cu5] complexes: inhibition and triggering of ligand arm hydrolysis and self-aggregation by chosen ancillary bridges. Dalton Transactions(47), pp. 17160-17176. (doi:10.1039/C8DT03390K) (PMID:30474684)

Das, M., Canaj, A. B. , Bertolasi, V., Murrie, M. and Ray, D. (2018) Strategic synthesis of [Cu2], [Cu4] and [Cu5] complexes: inhibition and triggering of ligand arm hydrolysis and self-aggregation by chosen ancillary bridges. Dalton Transactions(47), pp. 17160-17176. (doi:10.1039/C8DT03390K) (PMID:30474684)

[img] Text
173403.pdf - Accepted Version
Restricted to Repository staff only until 12 November 2019.

1MB

Abstract

The Schiff base ligand HL1 ({2,6-bis(allylimino)methyl}-4-methylphenol) having no coordinating donor arm has been examined for its reaction medium and ancillary bridge dependent reactivity for hierarchical family of CuII complexes. The ligand showed unique reactivity pattern toward CuII in solution. The bridging nature of in situ generated HO− ions in absence and presence of externally added carboxylates (RCOO−; R= CF3, C6H5 and CH3) has been utilized to produce complexes {[Cu2(µ–L2)2(H2O)]2[Cu2(µ–L2)2(H2O)2](ClO4)6} (1) (HL2 = 3-{(allylimino)methyl}-2-hydroxy-5-methylbenzaldehyde), [Cu4(µ4–O)(µ–L1)2(µ1,3–O2CCF3)4] (2), [Cu4(µ4–O)(µ–L1)2(µ1,3–O2CC6H5)4]∙H2O (3), [Cu5(µ3–OH)2(µ–L1)2(µ1,3–OAc)2(OAc)2(H2O)4][Cu5(µ3–OH)2(µ–L1)2(µ1,3–OAc)2(OAc)3(H2O)](ClO4)3∙2C2H5OH (4). Absence of carboxylate anions did not yield HO− ions in situ and triggered single ligand arm hydrolysis. The formation of tetra- and pentanuclear aggregates as well as ligand hydrolyzed dinulcear products has been rationalized to identify the possible roles of carboxylate anions in solution. Detailed characterization of the complexes in the solid state and in solution have been carried out using spectroscopic measurements, X-ray crystallography, variable temperature magnetic measurements and functional behavior. In MeOH solutions at 298 K, the complexes 1-4 showed catalytic oxidation of 3,5-di-tert-butyl catechol (3,5-DTBCH2) saturated with O2 of air.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Tsanai, Mr Angelos and Murrie, Professor Mark
Authors: Das, M., Canaj, A. B., Bertolasi, V., Murrie, M., and Ray, D.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Dalton Transactions
Publisher:Royal Society of Chemistry
ISSN:1477-9226
ISSN (Online):1477-9234
Published Online:12 November 2018

University Staff: Request a correction | Enlighten Editors: Update this record