Structure and thermal properties of volatile mixed-ligand magnesium complexes: Effect of tert-buryl and phenyl substitutes in a fluorinated β-diketonate

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Structure and thermal properties of volatile mixed-ligand magnesium complexes: Effect of tert-buryl and phenyl substitutes in a fluorinated β-diketonate. / Vikulova, E. S.; Sukhikh, A. S.; Mikhaylova, M. A. et al.

In: Journal of Structural Chemistry, Vol. 63, No. 8, 08.2022, p. 1323-1332.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{4f35858e9c2443afa061f3fc884f4c44,

title = "Structure and thermal properties of volatile mixed-ligand magnesium complexes: Effect of tert-buryl and phenyl substitutes in a fluorinated β-diketonate",

abstract = "Structures of volatile mixed-ligand complexes of magnesium with N,N,N′,N′-tetramethylethylenediamine (tmeda) and fluorinated β-diketonate ligands L = CF3C(O)CHC(O)R– (R = t-Bu (ptac) and Ph (btfac)) are determined. Complex [Mg(tmeda)(btfac)2] is obtained for the first time and is characterized by elemental analysis and IR spectrometry. Both [Mg(tmeda)(L)2] compounds are molecular complexes, and the symmetry of their crystals is increased due to the presence of an aromatic substituent: space groups Pccn (L = btfac) and P21/n (L = ptac). The magnesium atom occurs in a distorted octahedral environment of three chelate ligands. The bond lengths and chelate angles in both complexes are similar: d(Mg–N) = 2.226(2)-2.245(1) {\AA}, d(Mg–O) = 2.030(2)-2.043(2) {\AA}, θ(N–Mg–N) = 80.97(7)-81.68(10)°, θ(O–Mg–O) = 85.61(9)-85.75(7)°. The Hirshfeld surfaces (CrystalExplorer, Tonto) show a presence of weak intermolecular contacts C–HPh…F in the [Mg(tmeda)(btfac)2] packing (4 contacts per molecule). The qualitative order of volatility decrease for the complexes and their hexafluoroacetylacetonate analogue [Mg(tmeda)(hfac)2] (TGA and vacuum sublimation data) corresponds to the estimated energy increase of [Mg(tmeda)(L)2] crystal lattices (CrystalExplorer, B3LYP/6-31G(d,p)): L = hfac ~ ptac >> btfac.",

keywords = "diamine, magnesium, thermal analysis, volatile precursor, XRD, β-diketonate",

author = "Vikulova, {E. S.} and Sukhikh, {A. S.} and Mikhaylova, {M. A.} and Nazarova, {A. A.} and Zherikova, {K. V.} and Morozova, {N. B.}",

note = "Funding Information: The work was funded by the Russian Science Foundation (project 21-73-00252). Publisher Copyright: {\textcopyright} 2022, Pleiades Publishing, Ltd.",

year = "2022",

month = aug,

doi = "10.1134/S0022476622080133",

language = "English",

volume = "63",

pages = "1323--1332",

journal = "Journal of Structural Chemistry",

issn = "0022-4766",

publisher = "Springer GmbH & Co, Auslieferungs-Gesellschaf",

number = "8",

}

RIS

TY - JOUR

T1 - Structure and thermal properties of volatile mixed-ligand magnesium complexes: Effect of tert-buryl and phenyl substitutes in a fluorinated β-diketonate

AU - Vikulova, E. S.

AU - Sukhikh, A. S.

AU - Mikhaylova, M. A.

AU - Nazarova, A. A.

AU - Zherikova, K. V.

AU - Morozova, N. B.

PY - 2022/8

Y1 - 2022/8

N2 - Structures of volatile mixed-ligand complexes of magnesium with N,N,N′,N′-tetramethylethylenediamine (tmeda) and fluorinated β-diketonate ligands L = CF3C(O)CHC(O)R– (R = t-Bu (ptac) and Ph (btfac)) are determined. Complex [Mg(tmeda)(btfac)2] is obtained for the first time and is characterized by elemental analysis and IR spectrometry. Both [Mg(tmeda)(L)2] compounds are molecular complexes, and the symmetry of their crystals is increased due to the presence of an aromatic substituent: space groups Pccn (L = btfac) and P21/n (L = ptac). The magnesium atom occurs in a distorted octahedral environment of three chelate ligands. The bond lengths and chelate angles in both complexes are similar: d(Mg–N) = 2.226(2)-2.245(1) Å, d(Mg–O) = 2.030(2)-2.043(2) Å, θ(N–Mg–N) = 80.97(7)-81.68(10)°, θ(O–Mg–O) = 85.61(9)-85.75(7)°. The Hirshfeld surfaces (CrystalExplorer, Tonto) show a presence of weak intermolecular contacts C–HPh…F in the [Mg(tmeda)(btfac)2] packing (4 contacts per molecule). The qualitative order of volatility decrease for the complexes and their hexafluoroacetylacetonate analogue [Mg(tmeda)(hfac)2] (TGA and vacuum sublimation data) corresponds to the estimated energy increase of [Mg(tmeda)(L)2] crystal lattices (CrystalExplorer, B3LYP/6-31G(d,p)): L = hfac ~ ptac >> btfac.

AB - Structures of volatile mixed-ligand complexes of magnesium with N,N,N′,N′-tetramethylethylenediamine (tmeda) and fluorinated β-diketonate ligands L = CF3C(O)CHC(O)R– (R = t-Bu (ptac) and Ph (btfac)) are determined. Complex [Mg(tmeda)(btfac)2] is obtained for the first time and is characterized by elemental analysis and IR spectrometry. Both [Mg(tmeda)(L)2] compounds are molecular complexes, and the symmetry of their crystals is increased due to the presence of an aromatic substituent: space groups Pccn (L = btfac) and P21/n (L = ptac). The magnesium atom occurs in a distorted octahedral environment of three chelate ligands. The bond lengths and chelate angles in both complexes are similar: d(Mg–N) = 2.226(2)-2.245(1) Å, d(Mg–O) = 2.030(2)-2.043(2) Å, θ(N–Mg–N) = 80.97(7)-81.68(10)°, θ(O–Mg–O) = 85.61(9)-85.75(7)°. The Hirshfeld surfaces (CrystalExplorer, Tonto) show a presence of weak intermolecular contacts C–HPh…F in the [Mg(tmeda)(btfac)2] packing (4 contacts per molecule). The qualitative order of volatility decrease for the complexes and their hexafluoroacetylacetonate analogue [Mg(tmeda)(hfac)2] (TGA and vacuum sublimation data) corresponds to the estimated energy increase of [Mg(tmeda)(L)2] crystal lattices (CrystalExplorer, B3LYP/6-31G(d,p)): L = hfac ~ ptac >> btfac.

KW - diamine

KW - magnesium

KW - thermal analysis

KW - volatile precursor

KW - XRD

KW - β-diketonate

UR - http://www.scopus.com/inward/record.url?scp=85137500007&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/2410b1e9-7667-38d5-b21a-6306f311cce7/

U2 - 10.1134/S0022476622080133

DO - 10.1134/S0022476622080133

M3 - Article

AN - SCOPUS:85137500007

VL - 63

SP - 1323

EP - 1332

JO - Journal of Structural Chemistry

JF - Journal of Structural Chemistry

SN - 0022-4766

IS - 8

ER -

ID: 37140905