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Retention of the Cluster Core Structure during Ligand Exchange Reactions of Carboxylato-Substituted Metal Oxo Clusters.

Kreutzer J, Puchberger M, Artner C, Schubert U - Eur J Inorg Chem (2015)

Bottom Line: This was concluded from exchange/re-exchange experiments and from comparison of the IR bands of the cluster core of the original and ligand-exchanged clusters.The IR bands were assigned on the basis of DFT calculations.Scrambling reactions between two Zr4O2(OOCR)12 clusters with different carboxylato ligands are a new way to prepare mixed-ligand oxo clusters.

View Article: PubMed Central - PubMed

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

ABSTRACT

The exchange of the carboxylato ligands of Zr4O2(methacrylato)12 in reactions with carboxylic acids proceeds with retention of the composition and structure of the cluster core. This was concluded from exchange/re-exchange experiments and from comparison of the IR bands of the cluster core of the original and ligand-exchanged clusters. The IR bands were assigned on the basis of DFT calculations. Scrambling reactions between two Zr4O2(OOCR)12 clusters with different carboxylato ligands are a new way to prepare mixed-ligand oxo clusters.

No MeSH data available.


ATR-IR and calculated IR spectra in the MIR/FIR region of (a) Zr4 (sym) experimental, (b) Zr4 calculated, and (c) Zr4Piv experimental.
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fig05: ATR-IR and calculated IR spectra in the MIR/FIR region of (a) Zr4 (sym) experimental, (b) Zr4 calculated, and (c) Zr4Piv experimental.

Mentions: The agreement between the calculated and experimental spectrum of Zr4 is sufficiently good in terms of band position and band shape. The unscaled calculated frequencies are shifted slightly by ca. 5 % to higher wavenumbers (Table2 and Figure5). The IR bands of the methacrylato cluster Zr4 were assigned on the basis of the calculations and compared with those of the pivalato cluster Zr4Piv. The carboxylato stretching vibrations give strong bands in the range = 1600–1350 cm–1. Two additional strong bands at = 1100 and 1000 cm–1 were observed for Zr4Piv. The bands that support the intactness of the core are the asymmetric stretching vibration of the μO bridges of Zr4 at = 520 cm–1 (512 cm–1 calculated), which is only slightly shifted to = 524 cm–1 for Zr4Piv. The bands of the symmetric and asymmetric stretching of the Zr-μO core of Zr4 were observed at = 247 (calculated 263 cm–1) and 292 cm–1 (276 cm–1 calculated), respectively, and were shifted to = 228 and 257 cm–1 for Zr4Piv. The agreement of the most prominent IR bands of Zr4 and Zr4Piv, in particular the good agreement of the core vibrations, showed that the core was also preserved during the exchange reactions.


Retention of the Cluster Core Structure during Ligand Exchange Reactions of Carboxylato-Substituted Metal Oxo Clusters.

Kreutzer J, Puchberger M, Artner C, Schubert U - Eur J Inorg Chem (2015)

ATR-IR and calculated IR spectra in the MIR/FIR region of (a) Zr4 (sym) experimental, (b) Zr4 calculated, and (c) Zr4Piv experimental.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4471881&req=5

fig05: ATR-IR and calculated IR spectra in the MIR/FIR region of (a) Zr4 (sym) experimental, (b) Zr4 calculated, and (c) Zr4Piv experimental.
Mentions: The agreement between the calculated and experimental spectrum of Zr4 is sufficiently good in terms of band position and band shape. The unscaled calculated frequencies are shifted slightly by ca. 5 % to higher wavenumbers (Table2 and Figure5). The IR bands of the methacrylato cluster Zr4 were assigned on the basis of the calculations and compared with those of the pivalato cluster Zr4Piv. The carboxylato stretching vibrations give strong bands in the range = 1600–1350 cm–1. Two additional strong bands at = 1100 and 1000 cm–1 were observed for Zr4Piv. The bands that support the intactness of the core are the asymmetric stretching vibration of the μO bridges of Zr4 at = 520 cm–1 (512 cm–1 calculated), which is only slightly shifted to = 524 cm–1 for Zr4Piv. The bands of the symmetric and asymmetric stretching of the Zr-μO core of Zr4 were observed at = 247 (calculated 263 cm–1) and 292 cm–1 (276 cm–1 calculated), respectively, and were shifted to = 228 and 257 cm–1 for Zr4Piv. The agreement of the most prominent IR bands of Zr4 and Zr4Piv, in particular the good agreement of the core vibrations, showed that the core was also preserved during the exchange reactions.

Bottom Line: This was concluded from exchange/re-exchange experiments and from comparison of the IR bands of the cluster core of the original and ligand-exchanged clusters.The IR bands were assigned on the basis of DFT calculations.Scrambling reactions between two Zr4O2(OOCR)12 clusters with different carboxylato ligands are a new way to prepare mixed-ligand oxo clusters.

View Article: PubMed Central - PubMed

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

ABSTRACT

The exchange of the carboxylato ligands of Zr4O2(methacrylato)12 in reactions with carboxylic acids proceeds with retention of the composition and structure of the cluster core. This was concluded from exchange/re-exchange experiments and from comparison of the IR bands of the cluster core of the original and ligand-exchanged clusters. The IR bands were assigned on the basis of DFT calculations. Scrambling reactions between two Zr4O2(OOCR)12 clusters with different carboxylato ligands are a new way to prepare mixed-ligand oxo clusters.

No MeSH data available.