Synthesis and characterization of hydrophilic hydroxy-pyridinones and their complexes with molybdenum(VI)

Abstract

We have prepared four N-substituted hydroxypyridinones containing alcohol and morpholine groups. Complexes of the type cis-MoO2L2, where L represents the hydroxypyridinonato ligands have also been synthesized. The ethanolamine derivative, cis-MoO2(hep)2 (5), has been characterized by an X-ray diffraction study whereby the pyridinone ligands are bound to molybdenum in a cis bidentate fashion via the deprotonated hydroxy groups and the ketone moieties. Crystals of (5) are triclinic, with a 9.1930(7), b 14.2718(8), c 14.6219(9) Å, α 106.816(5), β 95.902(5), γ 96.350(5)°, Z 4, space group P–1.

Complexation of Molybdenum(VI) with Bis(3‐hydroxy‐4‐pyridinone)amino Acid Derivatives

“…290 nm (molar absorptivity ca. 2500  -1 cm -1 ), [16,20] this system could be studied by spectrophotometry. In this UV region, there are no measurable bands for the polyoxomolybdates and molybdate itself, [20] but for the ligand.…”

“…[30] For the hydroxypyridinone derivatives there is also a characteristic infrared four-band spectral pattern between 1610 and 1400 cm -1 . [16,31,32] Those bands can be assigned to ν C=O and ν ring that are very difficult to differentiate. Upon coordination, this pattern is usually preserved, but a bathochromic shift and a reordering of the peaks can be observed.…”

“…Furthermore, the bis(3,4-HP) ligands are expected to form stable 1:1 complexes, and so they are better suited for optimal complexation with the MoO 2 2+ unit (with four available coordination sites) than the corresponding monoderivatives. [15,16,19] Thus, we present herein a molybdenum(VI) complexation study with two bis(3,4-HP)amino acid derivatives recently reported. [11,12] These polydentate compounds have two 3,4-HP binding groups attached to linear hydrophilic aminocarboxylic backbones (see Scheme 1), namely iminodiacetic acid (IDA) and ethylenodiaminotetraacetic acid (EDTA), to give iminobis{acetyl[1-(3Ј-aminopropyl)-3-hydroxy-2-methyl-4-pyridinone]}, IDAPr(3,4-HP) 2 , and ethylenediamino-N,NЈ-bis(methylcarboxyl)-N,NЈ-bis{acetyl[1-(3Ј-aminopropyl)-3-hydroxy-2-methyl-4-pyridinone]}, EDTAPr(3,4-HP) 2 , respectively.…”

“…secretion of azotochelin by Azotobacter vinelandii), [14] and also as an insulin mimetic for the prevention or amelioration of cardiac dysfunction in diabetic hearts. [15] However, research on molybdenum(VI) complexation with 3,4-HPbased ligands is quite scarce and is limited to solid-state studies with monochelators, [14][15][16] which is in contrast to Mo complexation with other O,O-donor ligands (e.g. hydroxamate and cathecholate siderophore analogues, for which solution studies are known [14,17,18] ).…”

Μελέτη Συµπλόκων Των Στοιχείων Χαλκού, Μολυβδαινίου Και Κοβαλτίου Με Χηλικούς Υποκαταστάτες. Εφαρµογή Στη Θεραπεία Και Τη Διάγνωση

“…Τα σύµπλοκα του υποκαταστάτη αυτού µπορούν να χρησιµοποιηθούν ως µοντέλα για τη µελέτη βιολογικών αντιδράσεων[278][279][280][281]. Στην βιβλιογραφία έχουν χαρακτηριστεί µονοµερή σύµπλοκα του τύπου cis-MoO 2 L 2 , όπου L είναι ένας υδρόξυ-πυριδινονικός υποκαταστάτης[282][283][284].…”