Structure and Properties of Copper(II), Manganese(III), and Iron(III) Complexes with Potentially Pentaanionic Heptadentate Ligands Including Alkoxido, Amido, and Phenoxido Donors

Abstract

The synthesis and characterization of copper(II), manganese(III), and iron(III) complexes [Cu2(L1)(OAc)Cs2(MeOH)2]n (1), [Mn2(H3L1)2(OMe)2]·2MeOH (2), [Fe2(H3L1)2(Hpz)4](ClO4)2·2CH3CN (3), and [Fe2(H3L3)2(OMe)2]·8MeOH (4) of potentially pentaanionic heptadentate ligands,2‐hydroxy‐N‐{2‐hydroxy‐3‐[(2‐hydroxybenzoyl)amino]propyl}benzamide (H5L1) and 2‐hydroxy‐N‐{3‐hydroxy‐5‐[(2‐hydroxybenzoyl)amino]pentyl}benzamide (H5L3), are reported. The crystal structure and magnetic properties of these complexes have been determined. In complex 1, the ligand H5L1 acts as a heptadentate, fully deprotonated ligand, [L1]5–. In complexes 2, 3, and 4, H5L1 (2, 3) and H5L3 (4) act as tetradentate, partially deprotonated ligands, [H3L1]2– and [H3L3]2–.In complex 1, anionic [Cu2(L1)(OAc)]2– and cationic [Cs(MeOH)]+ units are linked through a quadruply bridging acetate ion and through the phenoxido‐oxygen and amido‐oxygen donor atoms of [L1]5– to yield a 2D polymeric network. Complexes 2–4 form extended supramolecular networks. Magnetic susceptibility data evidence antiferromagnetic interactions for 1, 2, and 4. The Fe···Fe distance is too long to allow measurable magnetic interactions in complex 3. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Alkali-Metal-Ion-Directed Self-Assembly of Redox-Active Manganese(III) Supramolecular Boxes

“…These intermolecular interactions are expected to be weaker than J because of the significantly greater distances involved. 36 In fact, because the introduction of an intermolecular interaction according to the mean-field Hamiltonian J = −2zJ⟨S z ⟩S z affords a marginal improvement to the fit of 3, only zero-field splittings were considered in order to avoid overparametrization.…”

(S)-2,2′-Dihydroxy-N,N′-(6-hydroxyhexane-1,5-diyl)dibenzamide

“…However, myxochelin A also forms stable ferric complexes in an acidic medium around pH 2-3. Under such conditions, a complete deprotonation of all four phenolic hydroxy groups is unfavourable and, alternatively, metal binding may rather occur in a bis-bidentate fashion via the two ortho-hydroxy-benzamide moieties (Cappillino et al, 2009;Stoicescu et al, 2009). For a direct investigation of such a coordination mode, we prepared dideoxy-myxochelin A as a model ligand and report here its crystal structure.…”

“…For the crystal structure of N,N 0 -(pentane-1,5-diyl)bis(3-methoxysalicylamide), see: Huang et al (1995). For metal complex formation with linear bis-catechol amides and linear bis-salicylamides, see: Duhme et al (1996); Huang et al (1995); Cappillino et al (2009); Stoicescu et al (2009). For the treatment of H atoms in SHELXL, see: Mü ller et al (2006).…”

Synthesis, Crystal Structure, and Magnetic Properties of a Very Rare Double μ‐1,1‐Azido‐ and a μ‐1,1‐(OMe)‐Bridged FeIII Dimer Containing a N,N,O‐Donor Tridentate Schiff Base Ligand

“…A plot of χ M T vs. T, for complex 2, where χ M is the magnetic susceptibility per formula unit, in the temperature range 2-300 K is shown in Figure 4. The χ M T value is [15] [c] mxba = m-xylylenebis(acetylacetone), ref. [16] [d] H 2 L = 2-salicyloylhydrazono-1,3-dithiolate, ref.…”