Synthesis and structure of [Mn6O2(O2CPh)10(EtOH)4(H2O)] ·. EtOH, a manganese aggregate containing three types of benzoate ligation. Isomerism in [Mn6O2(O2CPh)10] complexes

doi:10.1016/S0277-5387(00)83289-1

Polyhedron

Volume 11, Issue 2, 1992, Pages 251-255

https://doi.org/10.1016/S0277-5387(00)83289-1 Get rights and content

Abstract

The reaction of Mn(O₂CPh)₂·.4H₂O with KMnO₄ in warm ethanol in the presence of benzoic acid has been found to give, in addition to the previously reported “manganic benzoate”, the new hexanuclear mixed-valence manganese cluster [Mn₆O₂ (O₂CPh)₁₀(EtOH)₄(H₂O)]·.EtOH (1) in 40% yield. X-ray crystal structure determination at −172°C shows that the complex contains a distorted [Mn^II₄Mn^III₂O₂]¹⁰⁺ core and, in addition to terminal EtOH and H₂O groups, three different types of benzoate ligation viz. μ₃-bridging, μ₂-bridging and monodentate terminal forms.

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The use of methyl 2-pyridyl ketone oxime (mpkoH) in manganese benzoate chemistry is reported. The reaction of Mn(O₂CPh)₂ · 2H₂O with two equivalents of mpkoH in CH₂Cl₂ affords the mononuclear complex [Mn^II(O₂CPh)₂(mpkoH)₂] (2) in high yield. The Mn^II atom is coordinated by two monodentate ${PhCO}_{2}^{-}$ groups and two N,N′-bidentate mpkoH chelates in a cis–cis–trans fashion. Reaction mixtures comprising (NBuⁿ₄)[Mn^III₄O₂(O₂CPh)₉(H₂O)] and mpkoH in CH₂Cl₂, [Mn^IIMn^III₂O(O₂CPh)₆(py)₂(H₂O)] and mpkoH in CH₂Cl₂, or Mn(O₂CPh)₂ · 2H₂O, NBuⁿ₄ MnO₄ and mpkoH in MeOH/MeCN/CH₂Cl₂ all lead to the mixed-valent cluster [Mn^II₄Mn^III₄O₂(OH)₂(O₂CPh)₁₀(mpko)₄] (3) in moderate yields. The cluster molecule has the [Mn₈(μ₄-O)₂(μ₃-OH)₂]¹⁴⁺ core (another description of the core is [Mn₈(μ₄-O)₂(μ₃-OH)₂(μ-OR′′)₄(μ-ONR‴)₄]⁶⁺). Peripheral ligation is provided by two η¹, four η¹:η¹:μ and four η¹:η²:μ₃ ${PhCO}_{2}^{-}$ groups, as well as four η¹:η¹:η¹:μ mpko⁻ ligands. Variable-temperature, solid-state dc and ac magnetic studies were carried out on complex 3 in the 5.0–300 K (dc) and 1.8–10 K (ac) ranges. The data reveal dominant antiferromagnetic interactions and a resulting S = 0 ground state, which is rationalized in terms of the strong antiferromagnetic coupling within the central ${{Mn}_{2}^{III} O_{2}}^{2 +}$ subunit.
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The use of 1,3,5-trihydroxybenzene (thbH₃) in manganese carboxylate chemistry has been investigated. The reactions of thbH₃ with 4 and 6 equivalents of Mn(O₂CEt)₂ in MeOH afford the complexes [Mn₆(O₂CEt)₈(L)(MeOH)₄(H₂O)₂] (1) and [Mn₈O₂(O₂CEt)₁₄(MeOH)₄] (2), respectively. In the case of complex 1, the product of the in situ organic ligand transformation has been observed, namely the conversion of the tridentate thbH₃ group to a new octadentate ligand L⁴⁻; the latter has never been previously reported. Both complexes possess rare topologies, with 1 containing 6Mn^II ions, whereas 2 is mixed-valent 6Mn^II, 2Mn^III. The core of 1 consists of two [Mn₃(μ₃-OR)]⁵⁺ triangles linked by the bulky octadentate ligand L. The [Mn₈(μ₄-O)₂(μ-OR)₈]⁶⁺ core of 2 can be considered an extension of the common [Mn₆(μ₄-O)₂]¹⁰⁺ (4Mn^II, 2Mn^III) core, comprising two edge-sharing tetrahedra, with two additional Mn atoms at one end. Peripheral ligation in both 1 and 2 is provided by eight and fourteen bridging ${EtCO}_{2}^{-}$ groups, respectively. Variable-temperature, solid-state dc and ac magnetization studies were carried out on complexes 1 and 2 in the 1.8–300 K range. The magnetic susceptibility data for 1 were fit to the theoretical χ_M vs T expression, derived by the use of an isotropic Heisenberg spin Hamiltonian and the Van Vleck equation, for two essentially non-interacting triangular [Mn₃(μ₃-OR)(μ-OR)₂]³⁺ units. The fitting procedure revealed the two pairwise exchange parameters to be weakly ferromagnetic (J_basal = J′ = + 0.79(3) cm⁻¹) and antiferromagnetic (J_side = J = −2.04(3) cm⁻¹), respectively, resulting in an S = 5/2 spin ground state. In contrast, the data for 2 revealed dominant antiferromagnetic interactions and a resulting S = 0 ground state; the latter value is rationalized in terms of the strong antiferromagnetic coupling within the central ${Mn}_{2}^{III} O_{2}$ unit.
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Polyhedron

Abstract

References (12)

Adv. Inorg. Chem.

Angew. Chem., Int. Edn Engl.

Angew. Chem., Int. Edn Engl.

Ann. Rev. Plant Physiol. Molec. Biol.

Accts Chem. Res.

Inorg. Chem.

Cited by (31)

Heterometallic Fe<sup>III</sup>-Ce<sup>IV</sup> complexes from the use of aliphatic aminoalcohol ligands

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4-(Hydroxymethyl)pyridine and pyrimidine in manganese benzoate chemistry: Preparation and characterization of hexanuclear clusters featuring the { Mn<inf>4</inf><sup>II</sup> Mn<inf>2</inf><sup>III</sup> ( μ<inf>4</inf> - O )<inf>2</inf> }<sup>10 +</sup> core

High Nuclearity Clusters: Clusters and Aggregates with Paramagnetic Centers: Oxygen and Nitrogen Bridged Systems

Reductive coupling of trinuclear [Mn<sup>II</sup>Mn<inf>2</inf><sup>III</sup>,O] core to form hexanuclear [Mn<inf>4</inf><sup>II</sup>Mn <inf>2</inf><sup>III</sup>O<inf>2</inf>] cluster