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Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Hexanickel enediolate cluster generated in an acireductone dioxygenase model reaction
Katarzyna Rudzka1, Katarzyna Grubel, Atta M Arif
1Department of Chemistry and Biochemistry, Utah State University, Logan, Utah 84322-0300, USA.
Abstract:
A nickel(II) enediolate cluster (2) forms upon treatment of [(6-Ph(2)TPA)Ni(PhC(O)C(OH)C(O)Ph)]ClO(4) (1) with Me(4)NOH x 5 H(2)O in CH(3)CN. Crystallographic studies of 2 revealed a hexanuclear structure of S(6) symmetry with a formula of {[Ni(PhC(O)C(O)C(O)Ph)(CH(3)OH)] x 1.33 CH(3)OH}(6). Because isolation of bulk amounts of 2 from the reaction involving 1 proved impossible, a solvation analogue of 2 (labeled 5) was generated from admixture of Ni(ClO(4))(2) x 6 H(2)O, 2-hydroxy-1,3-diphenylpropane-1,3-dione, and Me(4)NOH x 5 H(2)O in CH(3)OH/CH(3)CN. Complex 5 is formulated as {[Ni(PhC(O)C(O)C(O)Ph)(H(2)O)] x H(2)O x 0.25 CH(3)CN}(6) based on elemental analysis, a molecular weight determination, UV-vis, and a magnetic moment measurement. Treatment of 5 with O(2) and 6-Ph(2)TPA (6 equiv) results in the formation of CO and [(6-Ph(2)TPA)Ni(O(2)CPh)(2)(H(2)O)] (3), the latter of which was isolated in 69% yield. The level of (18)O incorporation in this reaction matches that for a reaction wherein 2 is generated from 1. These results provide evidence that a nickel(II) enediolate cluster is the O(2) reactive species in a previously reported model reaction for nickel(II)-containing acireductone dioxygenase.
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