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Mixed-Metal Oxo Clusters Structurally Derived from Ti6O4(OR)8(OOCR')8.

Artner C, Koyun A, Czakler M, Schubert U - Eur J Inorg Chem (2014)

Bottom Line: The mixed-metal oxo clusters FeTi5O4(OiPr)4(OMc)10 (OMc = methacrylate), Zn2Ti4O4(OiPr)2(OMc)10, Cd4Ti2O2(OAc)2(OMc)10(HOiPr)2, [Ca2Ti4O4(OAc)2(OMc)10] n , and [Sr2Ti4O4(OMc)12(HOMc)2] n were obtained from the reaction of titanium alkoxides with the corresponding metal acetates and methacrylic acid.Their structures are derived from Ti clusters with the composition Ti6O4(OR)8(OOCR')8.The Ca and Sr derivatives consist of chains of condensed clusters.

View Article: PubMed Central - PubMed

Affiliation: Institute of Materials Chemistry, Vienna University of Technology Getreidemarkt 9, 1060 Vienna, Austria.

ABSTRACT

The mixed-metal oxo clusters FeTi5O4(OiPr)4(OMc)10 (OMc = methacrylate), Zn2Ti4O4(OiPr)2(OMc)10, Cd4Ti2O2(OAc)2(OMc)10(HOiPr)2, [Ca2Ti4O4(OAc)2(OMc)10] n , and [Sr2Ti4O4(OMc)12(HOMc)2] n were obtained from the reaction of titanium alkoxides with the corresponding metal acetates and methacrylic acid. Their structures are derived from Ti clusters with the composition Ti6O4(OR)8(OOCR')8. The Ca and Sr derivatives consist of chains of condensed clusters.

No MeSH data available.


Molecular structure ofTi6(μ3-O)2(μ2-O)2(μ2-OiPr)2(μ2-OMc)8(OiPr)6(Ti6): (top) ball-and-stick model; (bottom) polyhedral representation. Hydrogen atoms are omittedfor clarity. Selected bond lengths and angles: Ti1–Ti2 3.3783(3), Ti1–Ti3 3.1062(3),Ti2–Ti3 3.5862(4), Ti1–O1 1.9047(9), Ti1–O2 1.7497(9), Ti1–O3 2.0874(9),Ti1–O4 2.0024(10), Ti1–O6 2.0465(10), Ti1–O8 2.0051(10), Ti2–O21.8893(9), Ti2–O1 1.9061(9), Ti2–O5 2.1019(10), Ti2–O7 2.0892(10),Ti2–O10 2.0300(10), Ti2–O12 1.7598(11), Ti3–O1 2.0722(9), Ti3–O31.9572(10), Ti3–O9 2.1627(11), Ti3–O11 2.0482(11), Ti3–O13 1.7995(10),Ti3–O14 1.7903(11) Å; Ti1–O1–Ti2 128.00(5), Ti1–O1–Ti3102.63(4), Ti2–O1–Ti3 128.65(5)°.
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fig01: Molecular structure ofTi6(μ3-O)2(μ2-O)2(μ2-OiPr)2(μ2-OMc)8(OiPr)6(Ti6): (top) ball-and-stick model; (bottom) polyhedral representation. Hydrogen atoms are omittedfor clarity. Selected bond lengths and angles: Ti1–Ti2 3.3783(3), Ti1–Ti3 3.1062(3),Ti2–Ti3 3.5862(4), Ti1–O1 1.9047(9), Ti1–O2 1.7497(9), Ti1–O3 2.0874(9),Ti1–O4 2.0024(10), Ti1–O6 2.0465(10), Ti1–O8 2.0051(10), Ti2–O21.8893(9), Ti2–O1 1.9061(9), Ti2–O5 2.1019(10), Ti2–O7 2.0892(10),Ti2–O10 2.0300(10), Ti2–O12 1.7598(11), Ti3–O1 2.0722(9), Ti3–O31.9572(10), Ti3–O9 2.1627(11), Ti3–O11 2.0482(11), Ti3–O13 1.7995(10),Ti3–O14 1.7903(11) Å; Ti1–O1–Ti2 128.00(5), Ti1–O1–Ti3102.63(4), Ti2–O1–Ti3 128.65(5)°.

Mentions: Oxo clusters of the general compositionTiaOb(OR)c(OOCR′)dare obtained when titanium alkoxides, Ti(OR)4, are treated with more than one molarequivalent of a carboxylic acid.1 The carboxylic acid not onlyprovides carboxylate ligands but also acts as an in situ water source through esterification withthe eliminated alcohol. The outcome of the reaction depends, among others, on the groups R andR′ as well as the Ti(OR)4/R′COOH ratio. Many oxo clusters have beenisolated with different degrees of condensation (a:b ratio),different degrees of substitution (a:d ratio), differentproportions of residual OR groups (a:c ratio), and, as aconsequence, different structures. One of the more prominent structure types isTi6O4(OR)8(OOCR′)8, which was obtained forseveral R/R′ combinations.2,3 An example, with R = iPr and OOCR=OMc (Ti6) (HOMc= methacrylic acid), is shown in Figure1.


Mixed-Metal Oxo Clusters Structurally Derived from Ti6O4(OR)8(OOCR')8.

Artner C, Koyun A, Czakler M, Schubert U - Eur J Inorg Chem (2014)

Molecular structure ofTi6(μ3-O)2(μ2-O)2(μ2-OiPr)2(μ2-OMc)8(OiPr)6(Ti6): (top) ball-and-stick model; (bottom) polyhedral representation. Hydrogen atoms are omittedfor clarity. Selected bond lengths and angles: Ti1–Ti2 3.3783(3), Ti1–Ti3 3.1062(3),Ti2–Ti3 3.5862(4), Ti1–O1 1.9047(9), Ti1–O2 1.7497(9), Ti1–O3 2.0874(9),Ti1–O4 2.0024(10), Ti1–O6 2.0465(10), Ti1–O8 2.0051(10), Ti2–O21.8893(9), Ti2–O1 1.9061(9), Ti2–O5 2.1019(10), Ti2–O7 2.0892(10),Ti2–O10 2.0300(10), Ti2–O12 1.7598(11), Ti3–O1 2.0722(9), Ti3–O31.9572(10), Ti3–O9 2.1627(11), Ti3–O11 2.0482(11), Ti3–O13 1.7995(10),Ti3–O14 1.7903(11) Å; Ti1–O1–Ti2 128.00(5), Ti1–O1–Ti3102.63(4), Ti2–O1–Ti3 128.65(5)°.
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fig01: Molecular structure ofTi6(μ3-O)2(μ2-O)2(μ2-OiPr)2(μ2-OMc)8(OiPr)6(Ti6): (top) ball-and-stick model; (bottom) polyhedral representation. Hydrogen atoms are omittedfor clarity. Selected bond lengths and angles: Ti1–Ti2 3.3783(3), Ti1–Ti3 3.1062(3),Ti2–Ti3 3.5862(4), Ti1–O1 1.9047(9), Ti1–O2 1.7497(9), Ti1–O3 2.0874(9),Ti1–O4 2.0024(10), Ti1–O6 2.0465(10), Ti1–O8 2.0051(10), Ti2–O21.8893(9), Ti2–O1 1.9061(9), Ti2–O5 2.1019(10), Ti2–O7 2.0892(10),Ti2–O10 2.0300(10), Ti2–O12 1.7598(11), Ti3–O1 2.0722(9), Ti3–O31.9572(10), Ti3–O9 2.1627(11), Ti3–O11 2.0482(11), Ti3–O13 1.7995(10),Ti3–O14 1.7903(11) Å; Ti1–O1–Ti2 128.00(5), Ti1–O1–Ti3102.63(4), Ti2–O1–Ti3 128.65(5)°.
Mentions: Oxo clusters of the general compositionTiaOb(OR)c(OOCR′)dare obtained when titanium alkoxides, Ti(OR)4, are treated with more than one molarequivalent of a carboxylic acid.1 The carboxylic acid not onlyprovides carboxylate ligands but also acts as an in situ water source through esterification withthe eliminated alcohol. The outcome of the reaction depends, among others, on the groups R andR′ as well as the Ti(OR)4/R′COOH ratio. Many oxo clusters have beenisolated with different degrees of condensation (a:b ratio),different degrees of substitution (a:d ratio), differentproportions of residual OR groups (a:c ratio), and, as aconsequence, different structures. One of the more prominent structure types isTi6O4(OR)8(OOCR′)8, which was obtained forseveral R/R′ combinations.2,3 An example, with R = iPr and OOCR=OMc (Ti6) (HOMc= methacrylic acid), is shown in Figure1.

Bottom Line: The mixed-metal oxo clusters FeTi5O4(OiPr)4(OMc)10 (OMc = methacrylate), Zn2Ti4O4(OiPr)2(OMc)10, Cd4Ti2O2(OAc)2(OMc)10(HOiPr)2, [Ca2Ti4O4(OAc)2(OMc)10] n , and [Sr2Ti4O4(OMc)12(HOMc)2] n were obtained from the reaction of titanium alkoxides with the corresponding metal acetates and methacrylic acid.Their structures are derived from Ti clusters with the composition Ti6O4(OR)8(OOCR')8.The Ca and Sr derivatives consist of chains of condensed clusters.

View Article: PubMed Central - PubMed

Affiliation: Institute of Materials Chemistry, Vienna University of Technology Getreidemarkt 9, 1060 Vienna, Austria.

ABSTRACT

The mixed-metal oxo clusters FeTi5O4(OiPr)4(OMc)10 (OMc = methacrylate), Zn2Ti4O4(OiPr)2(OMc)10, Cd4Ti2O2(OAc)2(OMc)10(HOiPr)2, [Ca2Ti4O4(OAc)2(OMc)10] n , and [Sr2Ti4O4(OMc)12(HOMc)2] n were obtained from the reaction of titanium alkoxides with the corresponding metal acetates and methacrylic acid. Their structures are derived from Ti clusters with the composition Ti6O4(OR)8(OOCR')8. The Ca and Sr derivatives consist of chains of condensed clusters.

No MeSH data available.