Synthesis and Characterization of the First Group 2 Mixed β-Diketonate Alkoxide Complexes. X-ray Crystal Structures of [Ca4(tmhd)4(OEt)4(EtOH)4], [Ca4(tmhd)6(OCH2CH2NMe2)2], and [H2Ba4(tmhd)6(OCH2CH2OPri)4]

V. Cumaran Arunasalam; Ian Baxter; Simon R. Drake; Michael B. Hursthouse; K. M. Abdul Malik; David J. Otway

doi:10.1021/ic00125a032

Synthesis and Characterization of the First Group 2 Mixed β-Diketonate Alkoxide Complexes. X-ray Crystal Structures of [Ca₄(tmhd)₄(OEt)₄(EtOH)4], [Ca₄(tmhd)₆(OCH₂CH₂NMe₂)₂], and [H₂Ba₄(tmhd)₆(OCH₂CH₂OPrⁱ)₄]

V. Cumaran Arunasalam
, Ian Baxter
, Simon R. Drake
, Michael B. Hursthouse
, K. M. Abdul Malik
, David J. Otway

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

Abstract

The reaction of the ethanol-solvated metal ethoxides [M(OEt)₂(EtOH)₄]₈ (M = Ca, Sr, Ba) in n-hexane suspensions/ solutions with 1 equiv of a β-diketone, H-tmhd {H-tmhd is Bu^tCOC₂COBu^t}, yields the compounds [Ca₄-(tmhd)₄(OEt)₄(EtOH)₄] (1), [Sr(tmhd)(OEt)(EtOH)₀.₆₆]_n (2), and [Ba(tmhd)_1.5(OEt)_0.5(EtOH)_0.33]_n (3); further reaction of these complexes with a bifunctional alcohol yields the complexes [Ca₄(tmhd)₆(OCH₂CH₂NMe₂)₂] (4), [Ca(tmhd)_1.5(OCH₂CH₂OPrⁱ)_0.5]_n (5), [Sr(tmhd)(OCH₂CH₂NMe₂)]_n (6), [H_0.5Sr(tmhd)_1.5(OCH₂CH₂OMe)]_n (7), [H₂-Ba₄(tmhd)₆(OCH₂CH₂OPrⁱ)₄] (8), and [H_0.5Ba(tmhd)_1.5(OCH₂CH₂OMe)]_n (9) {the values of n are as yet unknown}. 1, 4, and 8 have also been characterized by X-ray crystallography. Crystal data: for 1, monoclinic space group P2₁\c, a = 14.781(2) Å, b = 26.959(7) Å, c = 20.443(2) Å, β = 110.60(2)°, γ = 4; for 4, monoclinic space group P2₁/n, a = 14.1803(7) Å, b = 12.047(3) Å, c = 25.114(5) Å, β = 100.64(1)°, γ = 2; for 8, monoclinic space group C2/c, a = 30.899(7) Å, b = 11.395(2) Å, c = 29.782(5) Å, β =103.08(1)°, γ = 4. Complexes 1, 4, and 8 are all tetrameric with a M₄O₄ structural motif; 1 has a cubane type structure while 4 and 8 are built from a ladder-like framework. All Ca atoms in 1 have very similar six-coordinate octahedral symmetry. The two unique Ca atoms in 4, which is centrosymmetric, are also six-coordinate, but one is octahedral and the other is trigonal prismatic. In complex 8, which is also centrosymmetric, the environments of the two unique Ba atoms are again different, one showing an eight-coordinate, bicapped trigonal prismatic and the other a nine-coordinate, monocapped square prismatic geometry. Compounds 1–9 may have properties pertinent for application as sol-gel precursors.

Original language	English
Pages (from-to)	5295-5306
Number of pages	12
Journal	Inorganic Chemistry
Volume	34
Issue number	21
DOIs	https://doi.org/10.1021/ic00125a032
Publication status	Published - 1 Oct 1995
Externally published	Yes

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Cumaran Arunasalam, V., Baxter, I., Drake, S. R., Hursthouse, M. B., Abdul Malik, K. M., & Otway, D. J. (1995). Synthesis and Characterization of the First Group 2 Mixed β-Diketonate Alkoxide Complexes. X-ray Crystal Structures of [Ca₄(tmhd)₄(OEt)₄(EtOH)4], [Ca₄(tmhd)₆(OCH₂CH₂NMe₂)₂], and [H₂Ba₄(tmhd)₆(OCH₂CH₂OPrⁱ)₄]. Inorganic Chemistry, 34(21), 5295-5306. https://doi.org/10.1021/ic00125a032

@article{e90155498b4048548f0071eba76868c8,

title = "Synthesis and Characterization of the First Group 2 Mixed β-Diketonate Alkoxide Complexes. X-ray Crystal Structures of [Ca4(tmhd)4(OEt)4(EtOH)4], [Ca4(tmhd)6(OCH2CH2NMe2)2], and [H2Ba4(tmhd)6(OCH2CH2OPri)4]",

abstract = "The reaction of the ethanol-solvated metal ethoxides [M(OEt)2(EtOH)4]8 (M = Ca, Sr, Ba) in n-hexane suspensions/ solutions with 1 equiv of a β-diketone, H-tmhd \{H-tmhd is ButCOC2COBut\}, yields the compounds [Ca4-(tmhd)4(OEt)4(EtOH)4] (1), [Sr(tmhd)(OEt)(EtOH)0.66]n (2), and [Ba(tmhd)1.5(OEt)0.5(EtOH)0.33]n (3); further reaction of these complexes with a bifunctional alcohol yields the complexes [Ca4(tmhd)6(OCH2CH2NMe2)2] (4), [Ca(tmhd)1.5(OCH2CH2OPri)0.5]n (5), [Sr(tmhd)(OCH2CH2NMe2)]n (6), [H0.5Sr(tmhd)1.5(OCH2CH2OMe)]n (7), [H2-Ba4(tmhd)6(OCH2CH2OPri)4] (8), and [H0.5Ba(tmhd)1.5(OCH2CH2OMe)]n (9) \{the values of n are as yet unknown\}. 1, 4, and 8 have also been characterized by X-ray crystallography. Crystal data: for 1, monoclinic space group P21\textbackslash{}c, a = 14.781(2) {\AA}, b = 26.959(7) {\AA}, c = 20.443(2) {\AA}, β = 110.60(2)°, γ = 4; for 4, monoclinic space group P21/n, a = 14.1803(7) {\AA}, b = 12.047(3) {\AA}, c = 25.114(5) {\AA}, β = 100.64(1)°, γ = 2; for 8, monoclinic space group C2/c, a = 30.899(7) {\AA}, b = 11.395(2) {\AA}, c = 29.782(5) {\AA}, β =103.08(1)°, γ = 4. Complexes 1, 4, and 8 are all tetrameric with a M4O4 structural motif; 1 has a cubane type structure while 4 and 8 are built from a ladder-like framework. All Ca atoms in 1 have very similar six-coordinate octahedral symmetry. The two unique Ca atoms in 4, which is centrosymmetric, are also six-coordinate, but one is octahedral and the other is trigonal prismatic. In complex 8, which is also centrosymmetric, the environments of the two unique Ba atoms are again different, one showing an eight-coordinate, bicapped trigonal prismatic and the other a nine-coordinate, monocapped square prismatic geometry. Compounds 1–9 may have properties pertinent for application as sol-gel precursors.",

author = "\{Cumaran Arunasalam\}, V. and Ian Baxter and Drake, \{Simon R.\} and Hursthouse, \{Michael B.\} and \{Abdul Malik\}, \{K. M.\} and Otway, \{David J.\}",

year = "1995",

month = oct,

day = "1",

doi = "10.1021/ic00125a032",

language = "English",

volume = "34",

pages = "5295--5306",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "21",

}

Cumaran Arunasalam, V, Baxter, I, Drake, SR, Hursthouse, MB, Abdul Malik, KM & Otway, DJ 1995, 'Synthesis and Characterization of the First Group 2 Mixed β-Diketonate Alkoxide Complexes. X-ray Crystal Structures of [Ca₄(tmhd)₄(OEt)₄(EtOH)4], [Ca₄(tmhd)₆(OCH₂CH₂NMe₂)₂], and [H₂Ba₄(tmhd)₆(OCH₂CH₂OPrⁱ)₄]', Inorganic Chemistry, vol. 34, no. 21, pp. 5295-5306. https://doi.org/10.1021/ic00125a032

Synthesis and Characterization of the First Group 2 Mixed β-Diketonate Alkoxide Complexes. X-ray Crystal Structures of [Ca₄(tmhd)₄(OEt)₄(EtOH)4], [Ca₄(tmhd)₆(OCH₂CH₂NMe₂)₂], and [H₂Ba₄(tmhd)₆(OCH₂CH₂OPrⁱ)₄]. / Cumaran Arunasalam, V.; Baxter, Ian; Drake, Simon R. et al.
In: Inorganic Chemistry, Vol. 34, No. 21, 01.10.1995, p. 5295-5306.

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

TY - JOUR

T1 - Synthesis and Characterization of the First Group 2 Mixed β-Diketonate Alkoxide Complexes. X-ray Crystal Structures of [Ca4(tmhd)4(OEt)4(EtOH)4], [Ca4(tmhd)6(OCH2CH2NMe2)2], and [H2Ba4(tmhd)6(OCH2CH2OPri)4]

AU - Cumaran Arunasalam, V.

AU - Baxter, Ian

AU - Drake, Simon R.

AU - Hursthouse, Michael B.

AU - Abdul Malik, K. M.

AU - Otway, David J.

PY - 1995/10/1

Y1 - 1995/10/1

N2 - The reaction of the ethanol-solvated metal ethoxides [M(OEt)2(EtOH)4]8 (M = Ca, Sr, Ba) in n-hexane suspensions/ solutions with 1 equiv of a β-diketone, H-tmhd {H-tmhd is ButCOC2COBut}, yields the compounds [Ca4-(tmhd)4(OEt)4(EtOH)4] (1), [Sr(tmhd)(OEt)(EtOH)0.66]n (2), and [Ba(tmhd)1.5(OEt)0.5(EtOH)0.33]n (3); further reaction of these complexes with a bifunctional alcohol yields the complexes [Ca4(tmhd)6(OCH2CH2NMe2)2] (4), [Ca(tmhd)1.5(OCH2CH2OPri)0.5]n (5), [Sr(tmhd)(OCH2CH2NMe2)]n (6), [H0.5Sr(tmhd)1.5(OCH2CH2OMe)]n (7), [H2-Ba4(tmhd)6(OCH2CH2OPri)4] (8), and [H0.5Ba(tmhd)1.5(OCH2CH2OMe)]n (9) {the values of n are as yet unknown}. 1, 4, and 8 have also been characterized by X-ray crystallography. Crystal data: for 1, monoclinic space group P21\c, a = 14.781(2) Å, b = 26.959(7) Å, c = 20.443(2) Å, β = 110.60(2)°, γ = 4; for 4, monoclinic space group P21/n, a = 14.1803(7) Å, b = 12.047(3) Å, c = 25.114(5) Å, β = 100.64(1)°, γ = 2; for 8, monoclinic space group C2/c, a = 30.899(7) Å, b = 11.395(2) Å, c = 29.782(5) Å, β =103.08(1)°, γ = 4. Complexes 1, 4, and 8 are all tetrameric with a M4O4 structural motif; 1 has a cubane type structure while 4 and 8 are built from a ladder-like framework. All Ca atoms in 1 have very similar six-coordinate octahedral symmetry. The two unique Ca atoms in 4, which is centrosymmetric, are also six-coordinate, but one is octahedral and the other is trigonal prismatic. In complex 8, which is also centrosymmetric, the environments of the two unique Ba atoms are again different, one showing an eight-coordinate, bicapped trigonal prismatic and the other a nine-coordinate, monocapped square prismatic geometry. Compounds 1–9 may have properties pertinent for application as sol-gel precursors.

AB - The reaction of the ethanol-solvated metal ethoxides [M(OEt)2(EtOH)4]8 (M = Ca, Sr, Ba) in n-hexane suspensions/ solutions with 1 equiv of a β-diketone, H-tmhd {H-tmhd is ButCOC2COBut}, yields the compounds [Ca4-(tmhd)4(OEt)4(EtOH)4] (1), [Sr(tmhd)(OEt)(EtOH)0.66]n (2), and [Ba(tmhd)1.5(OEt)0.5(EtOH)0.33]n (3); further reaction of these complexes with a bifunctional alcohol yields the complexes [Ca4(tmhd)6(OCH2CH2NMe2)2] (4), [Ca(tmhd)1.5(OCH2CH2OPri)0.5]n (5), [Sr(tmhd)(OCH2CH2NMe2)]n (6), [H0.5Sr(tmhd)1.5(OCH2CH2OMe)]n (7), [H2-Ba4(tmhd)6(OCH2CH2OPri)4] (8), and [H0.5Ba(tmhd)1.5(OCH2CH2OMe)]n (9) {the values of n are as yet unknown}. 1, 4, and 8 have also been characterized by X-ray crystallography. Crystal data: for 1, monoclinic space group P21\c, a = 14.781(2) Å, b = 26.959(7) Å, c = 20.443(2) Å, β = 110.60(2)°, γ = 4; for 4, monoclinic space group P21/n, a = 14.1803(7) Å, b = 12.047(3) Å, c = 25.114(5) Å, β = 100.64(1)°, γ = 2; for 8, monoclinic space group C2/c, a = 30.899(7) Å, b = 11.395(2) Å, c = 29.782(5) Å, β =103.08(1)°, γ = 4. Complexes 1, 4, and 8 are all tetrameric with a M4O4 structural motif; 1 has a cubane type structure while 4 and 8 are built from a ladder-like framework. All Ca atoms in 1 have very similar six-coordinate octahedral symmetry. The two unique Ca atoms in 4, which is centrosymmetric, are also six-coordinate, but one is octahedral and the other is trigonal prismatic. In complex 8, which is also centrosymmetric, the environments of the two unique Ba atoms are again different, one showing an eight-coordinate, bicapped trigonal prismatic and the other a nine-coordinate, monocapped square prismatic geometry. Compounds 1–9 may have properties pertinent for application as sol-gel precursors.

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U2 - 10.1021/ic00125a032

DO - 10.1021/ic00125a032

M3 - Article

AN - SCOPUS:0000910942

SN - 0020-1669

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SP - 5295

EP - 5306

JO - Inorganic Chemistry

JF - Inorganic Chemistry

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