DSC and vapour pressure investigation of some β-diketonates

Лазарев, В. Б.; Greenberg, J.H.; Ozerova, Z. P.; Sharpataya, G. A.

doi:10.1007/bf02138589

Cited by 7 publications

(8 citation statements)

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“…We repeated similar calculations for Cr(acac) 3 in ionic liquids for different heat of fusions and melting temperatures already reported in the literature. [48][49][50][51][52][53] We found a similarity with the results already obtained for V(acac) 3 . The solubility calculation for Cr(acac) 3 has been given in the ESI in Fig.…”

Section: Solubility Of Metal Complex In Ionic Liquidssupporting

confidence: 85%

Solubility model of metal complex in ionic liquids from first principle calculations

2019

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Section: Solubility Of Metal Complex In Ionic Liquidssupporting

confidence: 85%

Solubility model of metal complex in ionic liquids from first principle calculations

2019

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“…Thermochemical Properties . Table presents the results of our calorimetric measurements for the tris(acac) complexes with Al(III), Fe(III), Cr(III), Mn(III), and Co(III) together with the enthalpies of fusion, Δ fus H , and the melting points, T 0 , reported in other authors' papers. − The entropy of fusion, Δ fus S , has been calculated by dividing the enthalpy of fusion by the corresponding melting temperature, i.e., Δ fus S = Δ fus H / T 0 , and its values are also collected in Table .…”

Section: Resultsmentioning

confidence: 99%

“…Besides, a number of thermodynamic properties of metal(III) complexes with acetylacetonates, such as the enthalpy of fusion, − the melting point, ,,− the enthalpies of sublimation, ,− vaporization, ,, combustion, , and formation, , the heat capacity, and the metal−oxygen thermochemical bond energies, ,, have been measured to contribute to the knowledge of the physicochemical properties of this class of compounds. However, the reported properties differ in value and measuring procedure.…”

Section: Introductionmentioning

confidence: 99%

“…In this Article we present the results of new thermochemical measurements for M(acac) 3 complexes (M = Fe(III), Al(III), Cr(III), Mn(III), Co(III)) using differential scanning calorimetry (DSC) and evaluate them in relation to their different values found in the literature. − An MM model is proposed for this class of compounds. Geometry optimizations were performed in simulated crystalline surroundings.…”

Section: Introductionmentioning

confidence: 99%

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Is the Enthalpy of Fusion of Tris(acetylacetonato)metal(III) Complexes Affected by Their Potential Energy in the Crystal State?

et al. 2004

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In this Article we present enthalpies of fusion and melting points obtained from new thermochemical measurements of tris(acetylacetonato)metal(III), M(acac)(3), complexes (M = Fe, Al, Cr, Mn, Co) using differential scanning calorimetry (DSC) and evaluate them in relation to their different values found in the literature. An enthalpy of fusion of 27.67 kJ mol(-)(1) was derived for Mn(acac)(3) from a symmetrical DSC thermogram captured for the first time. The enthalpy value was indirectly confirmed with the solubility measurements of Mn(acac)(3) in acetylacetone. A hypothesis has been stated that the enthalpy of fusion and the potential energy of M(acac)(3) in the crystal state may be related. To calculate molecular in-crystal potential energy, in this Article we proposed a molecular mechanics model for the M(acac)(3) class of compounds. Nine X-ray crystal structures of M(acac)(3) complexes (M = Fe, Al, V, Mn, Co, Cr, Sc) were included in the modeling. The conformational potential energy was minimized for a molecule surrounded by other molecules in the crystal lattice. The partial charges from two schemes, the electrostatic potential (ESP) fit and the natural population analysis (NPA), were used to construct two types of force fields to examine which force field type would yield a better fit with the experimental thermal properties. The final force fields were named FF-ESP and FF-NPA. Both force field sets reproduced well the experimental crystal data of nine M(acac)(3) complexes as well as of tris(3-methyl-2,4-pentanedionato-O,O')cobalt(III). Only in-crystal potential energies derived by FF-NPA yielded a significant correlation (correlation coefficient R = -0.71) with the measured enthalpies of fusion. The enthalpy of fusion for Co(acac)(3) could not be determined experimentally because of simultaneous decomposition and fusion, and it is predicted to be 33.2 kJ mol(-)(1) from the correlation regression line.

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“…The results are summarized in Table 1. To date, there have been quite an impressive number of published measurements of vapor pressures and sublimation enthalpies for Al(acac) 3 , Cr(acac) 3 , and In(acac) 3 [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24]29,[47][48][49][50][51][52][53][54][55]. We compiled the relevant literature data, supplemented by our own for evaluation (Table 2).…”

Section: Vapor Pressurementioning

confidence: 99%

Breaking through the Thermodynamics “Wilds” of Metal–Organic Chemical Vapor Deposition Precursors: Metal tris-Acetylacetonates

Makarenko,

Trubin,

Zherikova

2023

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Metal acetylacetonates belong to the β-diketonate family and are considered as classics among precursors for metal–organic chemical vapor deposition (MOCVD). The success of film preparation is crucially dependent on the volatilization thermodynamics of the precursors used. Data on the volatilization thermodynamics of metal acetylacetonates are in huge disarray. We amassed and analyzed experimental data on the vapor pressures and on the enthalpies and entropies of fusion, vaporization, and sublimation of acetylacetonate tris-complexes of metals(III) (Al, Sc, Cr, Mn, Fe, Co, Ru, Rh, In, and Ir) available in the literary sources. In addition, saturated vapor pressures over crystalline Al(III), Cr(III), and In(III) acetylacetonates and corresponding thermodynamic sublimation properties were determined. New findings enabled us to arbitrate the conflict among literature data. The enthalpies and entropies of sublimation, vaporization, and fusion were adjusted to the reference temperature for a correct comparison using the empirically estimated differences in heat capacities. The heat capacity of the crystalline phase was shown to depend weakly on the metal atom. As a result, a reliable set of enthalpies and entropies of the mentioned processes of fundamental importance was derived for ten metal complexes. Relationships between volatility and structure were established depending on the central metal. The suggested algorithm can be fairly easily transferred to the acetylacetonate or other β-diketonate isoligand complexes with metals of different valence.

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DSC and vapour pressure investigation of some β-diketonates

Cited by 7 publications

References 0 publications

Solubility model of metal complex in ionic liquids from first principle calculations

Solubility model of metal complex in ionic liquids from first principle calculations

Is the Enthalpy of Fusion of Tris(acetylacetonato)metal(III) Complexes Affected by Their Potential Energy in the Crystal State?

Breaking through the Thermodynamics “Wilds” of Metal–Organic Chemical Vapor Deposition Precursors: Metal tris-Acetylacetonates

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