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Versatile Reactivity of Mn^II Complexes in Reactions with N-Donor Heterocycles: Metamorphosis of Labile Homometallic Pivalates vs. Assembling of Endurable Heterometallic Acetates.

ABSTRACT: Reaction of 2,2'-bipyridine (2,2'-bipy) or 1,10-phenantroline (phen) with [Mn(Piv)₂(EtOH)]_n led to the formation of binuclear complexes [Mn₂(Piv)₄L₂] (L = 2,2'-bipy (1), phen (2); Piv^- is the anion of pivalic acid). Oxidation of 1 or 2 by air oxygen resulted in the formation of tetranuclear Mn^II/III complexes [Mn₄O₂(Piv)₆L₂] (L = 2,2'-bipy (3), phen (4)). The hexanuclear complex [Mn₆(OH)₂(Piv)₁₀(pym)₄] (5) was formed in the reaction of [Mn(Piv)₂(EtOH)]_n with pyrimidine (pym), while oxidation of 5 produced the coordination polymer [Mn₆O₂(Piv)₁₀(pym)₂]_n (6). Use of pyrazine (pz) instead of pyrimidine led to the 2D-coordination polymer [Mn₄(OH)(Piv)₇(µ₂-pz)₂]_n (7). Interaction of [Mn(Piv)₂(EtOH)]_n with FeCl₃ resulted in the formation of the hexanuclear complex [Mn^II₄Fe^III₂O₂(Piv)₁₀(MeCN)₂(HPiv)₂] (8). The reactions of [MnFe₂O(OAc)₆(H₂O)₃] with 4,4'-bipyridine (4,4'-bipy) or trans-1,2-(4-pyridyl)ethylene (bpe) led to the formation of 1D-polymers [MnFe₂O(OAc)₆L₂]_n·2nDMF, where L = 4,4'-bipy (9·2DMF), bpe (10·2DMF) and [MnFe₂O(OAc)₆(bpe)(DMF)]_n·3.5nDMF (11·3.5DMF). All complexes were characterized by single-crystal X-ray diffraction. Desolvation of 11·3.5DMF led to a collapse of the porous crystal lattice that was confirmed by PXRD and N₂ sorption measurements, while alcohol adsorption led to porous structure restoration. Weak antiferromagnetic exchange was found in the case of binuclear Mn^II complexes (J_Mn-Mn = -1.03 cm^-1 for 1 and 2). According to magnetic data analysis (J_Mn-Mn = -(2.69 ÷ 0.42) cm^-1) and DFT calculations (J_Mn-Mn = -(6.9 ÷ 0.9) cm^-1) weak antiferromagnetic coupling between Mn^II ions also occurred in the tetranuclear {Mn₄(OH)(Piv)₇} unit of the 2D polymer 7. In contrast, strong antiferromagnetic coupling was found in oxo-bridged trinuclear fragment {MnFe₂O(OAc)₆} in 11·3.5DMF (J_Fe-Fe = -57.8 cm^-1, J_Fe-Mn = -20.12 cm^-1).

SUBMITTER: Polunin RA

PROVIDER: S-EPMC7919295 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature

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Versatile Reactivity of MnII Complexes in Reactions with N-Donor Heterocycles: Metamorphosis of Labile Homometallic Pivalates vs. Assembling of Endurable Heterometallic Acetates.

Polunin Ruslan A RA Evstifeev Igor S IS Cador Olivier O Golhen Stéphane S Gavrilenko Konstantin S KS Lytvynenko Anton S AS Efimov Nikolay N NN Minin Vadim V VV Bogomyakov Artem S AS Ouahab Lahcène L Kolotilov Sergey V SV Kiskin Mikhail A MA Eremenko Igor L IL

Molecules (Basel, Switzerland) 20210215 4

Reaction of 2,2'-bipyridine (2,2'-bipy) or 1,10-phenantroline (phen) with [Mn(Piv)2(EtOH)]n led to the formation of binuclear complexes [Mn2(Piv)4L2] (L = 2,2'-bipy (1), phen (2); Piv- is the anion of pivalic acid). Oxidation of 1 or 2 by air oxygen resulted in the formation of tetranuclear MnII/III complexes [Mn4O2(Piv)6L2] (L = 2,2'-bipy (< ...[more]

PMID: 33672016

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Project description:A novel series of mixed-valent, heteroleptic transition metal diketonates that can be utilized as prospective single-source precursors for the low-temperature preparation of oxide materials are reported. The first mixed-valent iron β-diketonates with different FeIII/FeII ratios have been synthesized by applying the mixed-ligand approach. Based on nearly quantitative reaction yields and analysis of iron-oxygen bonds, these compounds were formulated as [FeIII(acac)3][FeII(hfac)2] (1) and [FeII(hfac)2][FeIII(acac)3][FeII(hfac)2] (2). In the above heteroleptic complexes, the Lewis acidic, coordinatively unsaturated FeII centers chelated by two hfac (hexafluoroacetylacetonate) ligands with electron-withdrawing substituents maintain bridging interactions with oxygen atoms of electron-donating acac (acetylacetonate) groups that chelate the neighboring FeIII atoms. Switching the ligands on FeIII and FeII atoms in starting reagents resulted in the instant ligand exchange between iron centers and in yet another polynuclear homometallic diketonate [FeII(hfac)2][FeIII(acac)2(hfac)][FeII(hfac)2] (3) that adheres to the same bonding pattern as in complexes 1 and 2. The proposed synthetic methodology has been extended to design heterometallic diketonates with different M : M' ratios. Homometallic parent molecules have been used as templates to obtain heterometallic mixed-valent [FeIII(acac)3][MnII(hfac)2] (4) and [NiII(hfac)2][FeIII(acac)3][NiII(hfac)2] (5) complexes. The combination of two different diketonate ligands with electron-donating and electron-withdrawing substituents was found to be crucial for maintaining the above mixed-valent heterometallic assemblies. Theoretical investigation of two possible "isomers", [FeIII(acac)3][MnII(hfac)2] (4) and [MnIII(acac)3][FeII(hfac)2] (4') provided an additional support for the metal site assignment giving a preference of 9.78 kcal mol-1 for the molecule 4. Heterometallic complexes obtained in the course of this study have been found to act as effective single-source precursors for the synthesis of mixed-transition metal oxide materials M x M'2-xO3 and M x M'1-xO. The title highly volatile precursors can be used for the low-temperature preparation of both amorphous and crystalline heterometallic oxides in the form of thin films or nanosized particles that are known to operate as efficient catalysts in oxygen evolution reaction.

Dataset Information

Versatile Reactivity of Mn^II Complexes in Reactions with N-Donor Heterocycles: Metamorphosis of Labile Homometallic Pivalates vs. Assembling of Endurable Heterometallic Acetates.

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Versatile Reactivity of Mn<sup>II</sup> Complexes in Reactions with N-Donor Heterocycles: Metamorphosis of Labile Homometallic Pivalates vs. Assembling of Endurable Heterometallic Acetates.

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