Oxazolone copper(I) complexes inspired by the methanobactin active site

作者：Jahnke Ann Christin; Herter Anastasia; Dechert Sebastian; John Michael; Meyer Franc^*

来源：Inorganica Chimica Acta, 2011, 374(1): 601-605.

DOI：10.1016/j.ica.2011.03.070

• Copper
• Bioinorganic chemistry
• N ligands
• S ligands
• Oxazolone ligands
• Methanobactin

Two oxazolone-derived potential ligands with enethioether substituents have been synthesized that differ by the terminal thioether moiety (S-Et in L-1, S-C6H4(OMe)-2 in L-2). Both L-1 and L-2 behave as bidentate {NS} chelate ligands to form stable complexes with copper(I) triflate that crystallize as dimeric complexes [L2Cu2(OTf)(2)] (4 and 5) featuring a central {Cu2S2} diamond core with distinctly different Cu-S bonds. L-1 as well as 4 and 5 have been characterized by single crystal X-ray diffraction. NMR spectroscopy including H-1 and F-19 DOSY experiments reveals that 4 and 5 dissociate into monomeric species [LCu(OTf)] (40 and 5') in CDCl3 solutions. 4' and 5' retain the {NS} binding motif of the oxazolone-derived ligands, but are in slow equilibrium with their {OS} isomers 4 '' and 5 '' that result from E/Z isomerization of the exocyclic enethioether double bond.

• 出版日期2011-8-1