The thermochemistry and crystallography of the metal tris-acetylacetonates

Lalancette, Roger A.; Arslan, Evrim; Bernal, Ivan; Willhelm, Daniel; Grȩbowicz, Janusz; Pluta, M.

doi:10.1007/s10973-017-6799-x

Cited by 6 publications

(4 citation statements)

References 16 publications

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“…Generally, trivalent M III (acac) 3 complexes commonly exhibit solvent-and temperature-dependent crystalline polymorphism, which can lead to discrepant results between several groups or even between several preparations of the same compound. 70,71 5.3.2.2. Compound 6.…”

Section: Results and Analysismentioning

confidence: 99%

“…Differences between the present spectrum and that of Krzystek and co-workers are discussed in greater detail in the Supporting Information. Generally, trivalent M III (acac) 3 complexes commonly exhibit solvent- and temperature-dependent crystalline polymorphism, which can lead to discrepant results between several groups or even between several preparations of the same compound. , …”

Section: Results and Analysismentioning

confidence: 99%

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Investigations of the Magnetic and Spectroscopic Properties of V(III) and V(IV) Complexes

et al. 2018

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Herein, we utilize a variety of physical methods including magnetometry (SQUID), electron paramagnetic resonance (EPR), and magnetic circular dichroism (MCD), in conjunction with high-level ab initio theory to probe both the ground and ligand-field excited electronic states of a series of V(IV) ( S = /) and V(III) ( S = 1) molecular complexes. The ligand fields of the central metal ions are analyzed with the aid of ab initio ligand-field theory (AILFT), which allows for a chemically meaningful interpretation of multireference electronic structure calculations at the level of the complete-active-space self-consistent field with second-order N-electron valence perturbation theory. Our calculations are in good agreement with all experimentally investigated observables (magnetic properties, EPR, and MCD), making our extracted ligand-field theory parameters realistic. The ligand fields predicted by AILFT are further analyzed with conventional angular overlap parametrization, allowing the ligand field to be decomposed into individual σ- and π-donor contributions from individual ligands. The results demonstrate in VO complexes that while the axial vanadium-oxo interaction dominates both the ground- and excited-state properties of vanadyl complexes, proximal coordination can significantly modulate the vanadyl bond covalency. Similarly, the electronic properties of V(III) complexes are particularly sensitive to the available σ and π interactions with the surrounding ligands. The results of this study demonstrate the power of AILFT-based analysis and provide the groundwork for the future analysis of vanadium centers in homogeneous and heterogeneous catalysts.

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Section: Results and Analysismentioning

confidence: 99%

Section: Results and Analysismentioning

confidence: 99%

Investigations of the Magnetic and Spectroscopic Properties of V(III) and V(IV) Complexes

et al. 2018

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“…The crystal structure of the title compound (Figure 4) was obtained from a X‐ray diffraction measurement at a temperature of 110 K. The crystallographic information is provided in Tables S1 and S2 in the Supporting Information. Similar to the manganese (III) acetylacetonate complex Mn(acac) 3 , also the larger Mn(mesacac) 3 crystallizes in the monoclinic space group of P 2 1 / n with the unit cell containing four molecules [22] . The manganese center is surrounded by six oxygen atoms with two Mn−O distances of 2.116(1) Å and 2.145(1) Å along the z‐axis and four equatorial bond lengths between 1.9177(9) Å and 1.934(1) Å. Complexes with d 4 electronic configuration are well known for their Jahn‐Teller distortion, which was observed for Mn(acac) 3 [7a,b,8b] before, and is also clearly visible in the case of the Mn(mesacac) 3 .…”

Section: Resultsmentioning

confidence: 99%

“…Similar to the manganese (III) acetylacetonate complex Mn(acac) 3 , also the larger Mn(mesacac) 3 crystallizes in the monoclinic space group of P 2 1 / n with the unit cell containing four molecules. [22] The manganese center is surrounded by six oxygen atoms with two Mn−O distances of 2.116(1) Å and 2.145(1) Å along the z‐axis and four equatorial bond lengths between 1.9177(9) Å and 1.934(1) Å. Complexes with d 4 electronic configuration are well known for their Jahn‐Teller distortion, which was observed for Mn(acac) 3 [ 7a , 7b , 8b ] before, and is also clearly visible in the case of the Mn(mesacac) 3 . The octahedral elongation compared to the different Mn(acac) 3 structures known in the literature is slightly more pronounced.…”

Section: Resultsmentioning

confidence: 99%

Electronic Structure and Magnetic Properties of a High‐Spin Mn^IIIComplex: [Mn(mesacac)₃] (mesacac=1,3‐Bis(2,4,6‐trimethylphenyl)‐propane‐1,3‐dionato)

et al. 2022

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Metal acetylacetonates of the general formula [M(acac) 3 ] (M III = Cr, Mn, Fe, Co) are among the best investigated coordination compounds. Many of these first-row transition metal complexes are known to have unique electronic properties. Independently, photophysical research with different β-diketonate ligands pointed towards the possibility of a special effect of the 2,4,6trimethylphenyl substituted acetylacetonate (mesacac) on the electron distribution between ligand and metal (MLCT). We therefore synthesized and fully characterized the previously unknown octahedral title complex. Its solid-state structure shows a Jahn-Teller elongation with two MnÀ O bonds of 2.12/ 2.15 Å and four MnÀ O bonds of 1.93 Å. Thermogravimetric data show a thermal stability up to 270 °C. High-resolution mass spectroscopy helped to identify the decomposition pathways. The electronic state and spin configuration of manganese were characterized with a focus on its magnetic properties by measurement of the magnetic susceptibility and triple-zeta density functional theory (DFT) calculations. The high-spin state of manganese was confirmed by the determination of an effective magnetic moment of 4.85 μ B for the manganese center.

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The thermal decomposition and analyses of metal tris-acetylacetonates

Lalancette

Syzdek

Grȩbowicz

et al. 2018

J Therm Anal Calorim

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The thermochemistry and crystallography of the metal tris-acetylacetonates

Cited by 6 publications

References 16 publications

Investigations of the Magnetic and Spectroscopic Properties of V(III) and V(IV) Complexes

Investigations of the Magnetic and Spectroscopic Properties of V(III) and V(IV) Complexes

Electronic Structure and Magnetic Properties of a High‐Spin Mn^IIIComplex: [Mn(mesacac)₃] (mesacac=1,3‐Bis(2,4,6‐trimethylphenyl)‐propane‐1,3‐dionato)

The thermal decomposition and analyses of metal tris-acetylacetonates

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The thermochemistry and crystallography of the metal tris-acetylacetonates

Cited by 6 publications

References 16 publications

Investigations of the Magnetic and Spectroscopic Properties of V(III) and V(IV) Complexes

Investigations of the Magnetic and Spectroscopic Properties of V(III) and V(IV) Complexes

Electronic Structure and Magnetic Properties of a High‐Spin MnIIIComplex: [Mn(mesacac)3] (mesacac=1,3‐Bis(2,4,6‐trimethylphenyl)‐propane‐1,3‐dionato)

The thermal decomposition and analyses of metal tris-acetylacetonates

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Electronic Structure and Magnetic Properties of a High‐Spin Mn^IIIComplex: [Mn(mesacac)₃] (mesacac=1,3‐Bis(2,4,6‐trimethylphenyl)‐propane‐1,3‐dionato)