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Acetic Acid Mediated Synthesis of Phosphonate-Substituted Titanium Oxo Clusters.

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

Bottom Line: The clusters [Ti6O4(OiPr)10(OAc)2(O3PR)2] (OAc = acetate) were obtained for a large variety of functional and non-functional groups R under a range of reaction conditions.This cluster type, which is also retained in solution, therefore appears to be very robust.Two other clusters, [Ti5O(OiPr)11(OAc)(O3PCH2CH2CH2Br)3] and [Ti5O3(OiPr)6(OAc)4(O3P-xylyl)2], were only isolated in special cases.

View Article: PubMed Central - PubMed

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

ABSTRACT

New phosphonate/acetate-substituted titanium oxo/alkoxo clusters were prepared from Ti(OiPr)4 and bis(trimethylsilyl) phosphonates in the presence of acetic acid, which served to generate water in situ through ester formation. The process led to clusters with a higher degree of condensation than in previously known phosphonate-substituted titanium oxo clusters. The clusters [Ti6O4(OiPr)10(OAc)2(O3PR)2] (OAc = acetate) were obtained for a large variety of functional and non-functional groups R under a range of reaction conditions. This cluster type, which is also retained in solution, therefore appears to be very robust. Two other clusters, [Ti5O(OiPr)11(OAc)(O3PCH2CH2CH2Br)3] and [Ti5O3(OiPr)6(OAc)4(O3P-xylyl)2], were only isolated in special cases.

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Molecular structure of[Ti6(μ3-O)2(μ2-O)2(μ2-OiPr)4(OiPr)6(OAc)2(O3PEt)2](1). Hydrogen atoms are omitted for clarity.
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fig01: Molecular structure of[Ti6(μ3-O)2(μ2-O)2(μ2-OiPr)4(OiPr)6(OAc)2(O3PEt)2](1). Hydrogen atoms are omitted for clarity.

Mentions: Reaction of one molar equivalent of bis(trimethylsilyl) ethylphosphonate with two equivalents ofacetic acid and four equivalents of Ti(OiPr)4 led to the centrosymmetriccluster[Ti6(μ3-O)2(μ2-O)2(μ2-OiPr)4(OiPr)6(OAc)2(O3PEt)2](1; Figure1, OAc = acetate), with a highdegree of condensation (0.67). The cluster was, to the best of our knowledge, also the first mixedcarboxylate-phosphonate titanium oxo cluster to be characterized. This new cluster type consists ofa Ti6O4 cluster core with two parallel Ti3O triangles connected byμ2-oxo and phosphonate bridges. The nearly cubicTi6P2O10 core resembles that of polyhedral oligomericsilsesquioxanes (POSS) with a Si8O12 core. The titanium and phosphorus atomsform a distorted parallelepiped (Figure2).


Acetic Acid Mediated Synthesis of Phosphonate-Substituted Titanium Oxo Clusters.

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

Molecular structure of[Ti6(μ3-O)2(μ2-O)2(μ2-OiPr)4(OiPr)6(OAc)2(O3PEt)2](1). Hydrogen atoms are omitted for clarity.
© Copyright Policy
Related In: Results  -  Collection

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getmorefigures.php?uid=PMC4362471&req=5

fig01: Molecular structure of[Ti6(μ3-O)2(μ2-O)2(μ2-OiPr)4(OiPr)6(OAc)2(O3PEt)2](1). Hydrogen atoms are omitted for clarity.
Mentions: Reaction of one molar equivalent of bis(trimethylsilyl) ethylphosphonate with two equivalents ofacetic acid and four equivalents of Ti(OiPr)4 led to the centrosymmetriccluster[Ti6(μ3-O)2(μ2-O)2(μ2-OiPr)4(OiPr)6(OAc)2(O3PEt)2](1; Figure1, OAc = acetate), with a highdegree of condensation (0.67). The cluster was, to the best of our knowledge, also the first mixedcarboxylate-phosphonate titanium oxo cluster to be characterized. This new cluster type consists ofa Ti6O4 cluster core with two parallel Ti3O triangles connected byμ2-oxo and phosphonate bridges. The nearly cubicTi6P2O10 core resembles that of polyhedral oligomericsilsesquioxanes (POSS) with a Si8O12 core. The titanium and phosphorus atomsform a distorted parallelepiped (Figure2).

Bottom Line: The clusters [Ti6O4(OiPr)10(OAc)2(O3PR)2] (OAc = acetate) were obtained for a large variety of functional and non-functional groups R under a range of reaction conditions.This cluster type, which is also retained in solution, therefore appears to be very robust.Two other clusters, [Ti5O(OiPr)11(OAc)(O3PCH2CH2CH2Br)3] and [Ti5O3(OiPr)6(OAc)4(O3P-xylyl)2], were only isolated in special cases.

View Article: PubMed Central - PubMed

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

ABSTRACT

New phosphonate/acetate-substituted titanium oxo/alkoxo clusters were prepared from Ti(OiPr)4 and bis(trimethylsilyl) phosphonates in the presence of acetic acid, which served to generate water in situ through ester formation. The process led to clusters with a higher degree of condensation than in previously known phosphonate-substituted titanium oxo clusters. The clusters [Ti6O4(OiPr)10(OAc)2(O3PR)2] (OAc = acetate) were obtained for a large variety of functional and non-functional groups R under a range of reaction conditions. This cluster type, which is also retained in solution, therefore appears to be very robust. Two other clusters, [Ti5O(OiPr)11(OAc)(O3PCH2CH2CH2Br)3] and [Ti5O3(OiPr)6(OAc)4(O3P-xylyl)2], were only isolated in special cases.

No MeSH data available.


Related in: MedlinePlus