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Mixed-valent, heteroleptic homometallic diketonates as templates for the design of volatile heterometallic precursors.

ABSTRACT: 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 ?-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.

SUBMITTER: Lieberman CM

PROVIDER: S-EPMC5654368 | biostudies-literature | 2015 May

REPOSITORIES: biostudies-literature

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Mixed-valent, heteroleptic homometallic diketonates as templates for the design of volatile heterometallic precursors.

Lieberman Craig M CM Filatov Alexander S AS Wei Zheng Z Rogachev Andrey Yu AY Abakumov Artem M AM Dikarev Evgeny V EV

Chemical science 20150225 5

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) ...[more]

PMID: 29142682

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Project description:We describe a synthetic strategy for the preparation of bis-heteroleptic polypyridyl Ru(II) complexes of the type [Ru(L1)2(L2)]2+ (L1 and L2 = diimine ligands) from well-defined Ru(II) precursors. For this purpose, a series of six neutral, anionic, and cationic cis-locked Ru(II)-DMSO complexes (2-7) of the general formula [Y] fac-[RuX(DMSO-S)3(O-O)]n (where O-O is a symmetrical chelating anion: oxalate (ox), malonate (mal), acetylacetonate (acac); X = DMSO-O or Cl-; n = -1/0/+1 depending on the nature and charge of X and O-O; when present, Y = K+ or PF6-) were efficiently prepared from the well-known cis-[RuCl2(DMSO)4] (1). When treated with diimine chelating ligands (L1 = bpy, phen, dpphen), the compounds 2-7 afforded the target [Ru(L1)2(O-O)]0/+ complex together with the undesired (and unexpected) [Ru(L1)3]2+ species. Nevertheless, we found that the formation of [Ru(L1)3]2+can be minimized by carefully adjusting the reaction conditions: in particular, high selectivity toward [Ru(L1)2(O-O)]0/+ and almost complete conversion of the precursor was obtained within minutes, also on a 100-200 mg scale, when the reactions were performed in absolute ethanol at 150 °C in a microwave reactor. Depending on the nature of L1 and concentration, with the oxalate and malonate precursors, the neutral product [Ru(L1)2(O-O)] can precipitate spontaneously from the final mixture, in pure form and acceptable-to-good yields. When spontaneous precipitation of the disubstituted product does not occur, purification from [Ru(L1)3]2+ can be rather easily accomplished by column chromatography or solvent extraction. By comparison, under the same conditions, compound 1 is much less selective, thus demonstrating that locking the geometry of the precursor through the introduction of O-O in the coordination sphere of Ru is a valid strategic approach. By virtue of its proton-sensitive nature, facile and quantitative replacement of O-O in [Ru(L1)2(O-O)]0/+ by L2, selectively affording [Ru(L1)2(L2)]2+, was accomplished in refluxing ethanol in the presence of a slight excess of trifluoroacetic acid or HPF6.

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Mixed-valent, heteroleptic homometallic diketonates as templates for the design of volatile heterometallic precursors.

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Mixed-valent, heteroleptic homometallic diketonates as templates for the design of volatile heterometallic precursors.

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