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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.


1H–13C HMBC spectra ([D8]toluene, –80 °C) of (a) Zr4, (b) Zr4Piv (crystals obtained from the exchange experiment), and (c) Zr4 after re-exchange.
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fig03: 1H–13C HMBC spectra ([D8]toluene, –80 °C) of (a) Zr4, (b) Zr4Piv (crystals obtained from the exchange experiment), and (c) Zr4 after re-exchange.

Mentions: The 1H–13C HMBC spectrum of Zr4 at –80 °C (see Figure3, a) shows four sets of chemically inequivalent signals in agreement with the C2h molecular symmetry of Zr4 (sym) as has been discussed previously.[14] The three highfield peaks (δ =173.2, 174.2, and 181.1 ppm) correspond to the bridging OMc ligands of Zr4, and the fourth peak at δ = 186.7 ppm is attributed to the chelating ligand. The same splitting into four sets of peaks is found for the Zr4Piv cluster (Figure3, b). Here, the bridging pivalato ligands give cross-peaks at δ = 185.89, 186.28, and 193.96 ppm, and the chelating pivalato ligand gives a cross-peak at δ = 199.3 ppm (see Figure3, b).


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)

1H–13C HMBC spectra ([D8]toluene, –80 °C) of (a) Zr4, (b) Zr4Piv (crystals obtained from the exchange experiment), and (c) Zr4 after re-exchange.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

fig03: 1H–13C HMBC spectra ([D8]toluene, –80 °C) of (a) Zr4, (b) Zr4Piv (crystals obtained from the exchange experiment), and (c) Zr4 after re-exchange.
Mentions: The 1H–13C HMBC spectrum of Zr4 at –80 °C (see Figure3, a) shows four sets of chemically inequivalent signals in agreement with the C2h molecular symmetry of Zr4 (sym) as has been discussed previously.[14] The three highfield peaks (δ =173.2, 174.2, and 181.1 ppm) correspond to the bridging OMc ligands of Zr4, and the fourth peak at δ = 186.7 ppm is attributed to the chelating ligand. The same splitting into four sets of peaks is found for the Zr4Piv cluster (Figure3, b). Here, the bridging pivalato ligands give cross-peaks at δ = 185.89, 186.28, and 193.96 ppm, and the chelating pivalato ligand gives a cross-peak at δ = 199.3 ppm (see Figure3, b).

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.