Beryllium Chelation by Dicarboxylic Acids in Aqueous Solution

Michael Schmidt; Andreas Bauer; Hubert Schmidbaur

doi:10.1021/ic961410k

Beryllium Chelation by Dicarboxylic Acids in Aqueous Solution

Michael Schmidt, Andreas Bauer, Hubert Schmidbaur

Department of Chemistry

Technical University of Munich

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

37 Scopus citations

Abstract

Maleic and phthalic acids are found to react with Be(OH)₂, generated in situ from BeSO₄(aq) and Ba(OH)₂(aq), in aqueous solution at pH 3.0 or 4.4, respectively (25°C), to give solutions containing the complexes (H₂O)₂Be[(OOCCH)₂] (1) and (H₂O)₂Be[(OOC)₂C₆H₄] (3). The products can be isolated in high yield and identified by microanalytical data. With 2 equiv of the dicarboxylic acids and the pH adjusted to 5.5 and 5.9, respectively, by addition of ammonia, the bis-chelate complexes [(NH₄)⁺]₂{[Be[(OOCCH)₂] ₂}^2- (2) and [(NH₄)⁺]₂{Be[(OOC)₂C ₆H₄]₂}^2- (4) are obtained, which can also be isolated. The compounds show distinct ⁹Be, ¹H, and ¹³C resonances in their NMR spectra in aqueous solutions. Layering of an aqueous solution of compound 4 with acetone at ambient temperature leads to the precipitation of single crystals suitable for an X-ray structure determination. This salt (5) was found to contain the bis-chelated dianion {Be[(OOC)₂C₆H₄]₂}^2- with the beryllium atom in the spiro center of two seven-membered rings and an overall geometry approaching closely C₂ symmetry. These anions are associated with two crystallographically independent but structurally similar counterions [MeC(O)CH₂CMe₂NH₃]⁺, which are the product of a condensation reaction of the ammonium cation with the acetone solvent. In the crystal the ammonium hydrogen atoms of the cations form N-H⋯O hydrogen bonds with the oxo functions of the dianion.

Original language	English
Pages (from-to)	2040-2043
Number of pages	4
Journal	Inorganic Chemistry
Volume	36
Issue number	10
DOIs	https://doi.org/10.1021/ic961410k
State	Published - 1997

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@article{c2fc2302b58640adb8dc6d9e6cf5242e,

title = "Beryllium Chelation by Dicarboxylic Acids in Aqueous Solution",

abstract = "Maleic and phthalic acids are found to react with Be(OH)2, generated in situ from BeSO4(aq) and Ba(OH)2(aq), in aqueous solution at pH 3.0 or 4.4, respectively (25°C), to give solutions containing the complexes (H2O)2Be[(OOCCH)2] (1) and (H2O)2Be[(OOC)2C6H4] (3). The products can be isolated in high yield and identified by microanalytical data. With 2 equiv of the dicarboxylic acids and the pH adjusted to 5.5 and 5.9, respectively, by addition of ammonia, the bis-chelate complexes [(NH4)+]2{[Be[(OOCCH)2] 2}2- (2) and [(NH4)+]2{Be[(OOC)2C 6H4]2}2- (4) are obtained, which can also be isolated. The compounds show distinct 9Be, 1H, and 13C resonances in their NMR spectra in aqueous solutions. Layering of an aqueous solution of compound 4 with acetone at ambient temperature leads to the precipitation of single crystals suitable for an X-ray structure determination. This salt (5) was found to contain the bis-chelated dianion {Be[(OOC)2C6H4]2}2- with the beryllium atom in the spiro center of two seven-membered rings and an overall geometry approaching closely C2 symmetry. These anions are associated with two crystallographically independent but structurally similar counterions [MeC(O)CH2CMe2NH3]+, which are the product of a condensation reaction of the ammonium cation with the acetone solvent. In the crystal the ammonium hydrogen atoms of the cations form N-H⋯O hydrogen bonds with the oxo functions of the dianion.",

author = "Michael Schmidt and Andreas Bauer and Hubert Schmidbaur",

year = "1997",

doi = "10.1021/ic961410k",

language = "English",

volume = "36",

pages = "2040--2043",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "10",

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TY - JOUR

T1 - Beryllium Chelation by Dicarboxylic Acids in Aqueous Solution

AU - Schmidt, Michael

AU - Bauer, Andreas

AU - Schmidbaur, Hubert

PY - 1997

Y1 - 1997

N2 - Maleic and phthalic acids are found to react with Be(OH)2, generated in situ from BeSO4(aq) and Ba(OH)2(aq), in aqueous solution at pH 3.0 or 4.4, respectively (25°C), to give solutions containing the complexes (H2O)2Be[(OOCCH)2] (1) and (H2O)2Be[(OOC)2C6H4] (3). The products can be isolated in high yield and identified by microanalytical data. With 2 equiv of the dicarboxylic acids and the pH adjusted to 5.5 and 5.9, respectively, by addition of ammonia, the bis-chelate complexes [(NH4)+]2{[Be[(OOCCH)2] 2}2- (2) and [(NH4)+]2{Be[(OOC)2C 6H4]2}2- (4) are obtained, which can also be isolated. The compounds show distinct 9Be, 1H, and 13C resonances in their NMR spectra in aqueous solutions. Layering of an aqueous solution of compound 4 with acetone at ambient temperature leads to the precipitation of single crystals suitable for an X-ray structure determination. This salt (5) was found to contain the bis-chelated dianion {Be[(OOC)2C6H4]2}2- with the beryllium atom in the spiro center of two seven-membered rings and an overall geometry approaching closely C2 symmetry. These anions are associated with two crystallographically independent but structurally similar counterions [MeC(O)CH2CMe2NH3]+, which are the product of a condensation reaction of the ammonium cation with the acetone solvent. In the crystal the ammonium hydrogen atoms of the cations form N-H⋯O hydrogen bonds with the oxo functions of the dianion.

AB - Maleic and phthalic acids are found to react with Be(OH)2, generated in situ from BeSO4(aq) and Ba(OH)2(aq), in aqueous solution at pH 3.0 or 4.4, respectively (25°C), to give solutions containing the complexes (H2O)2Be[(OOCCH)2] (1) and (H2O)2Be[(OOC)2C6H4] (3). The products can be isolated in high yield and identified by microanalytical data. With 2 equiv of the dicarboxylic acids and the pH adjusted to 5.5 and 5.9, respectively, by addition of ammonia, the bis-chelate complexes [(NH4)+]2{[Be[(OOCCH)2] 2}2- (2) and [(NH4)+]2{Be[(OOC)2C 6H4]2}2- (4) are obtained, which can also be isolated. The compounds show distinct 9Be, 1H, and 13C resonances in their NMR spectra in aqueous solutions. Layering of an aqueous solution of compound 4 with acetone at ambient temperature leads to the precipitation of single crystals suitable for an X-ray structure determination. This salt (5) was found to contain the bis-chelated dianion {Be[(OOC)2C6H4]2}2- with the beryllium atom in the spiro center of two seven-membered rings and an overall geometry approaching closely C2 symmetry. These anions are associated with two crystallographically independent but structurally similar counterions [MeC(O)CH2CMe2NH3]+, which are the product of a condensation reaction of the ammonium cation with the acetone solvent. In the crystal the ammonium hydrogen atoms of the cations form N-H⋯O hydrogen bonds with the oxo functions of the dianion.

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U2 - 10.1021/ic961410k

DO - 10.1021/ic961410k

M3 - Article

AN - SCOPUS:0001101482

SN - 0020-1669

VL - 36

SP - 2040

EP - 2043

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 10

ER -

Beryllium Chelation by Dicarboxylic Acids in Aqueous Solution

Abstract

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