Coordination variety of phenyltetrazolato and dimethylamido ligands in dimeric Ti, Zr, and Ta complexes

Three structurally diverse 5-phenyltetrazolato (Tz) Ti, Zr, and Ta complexes, namely, (C<sub>2</sub>H<sub>8</sub>N)[Ti<sub>2</sub>(C<sub>7</sub>H<sub>5</sub>N<sub>4</sub>)<sub>5</sub>(C<sub>2</sub>H<sub>6</sub>N)<sub>4</sub>]·1.45C<sub>6</sub>H<sub>6</sub> or (Me<sub>2</sub>NH<sub>2</sub>)[Ti<sub>2</sub>(NMe<sub>2</sub>)<sub>4</sub>(2,3-μ-Tz)<sub>3</sub>(2-η<sup>1</sup>-Tz)<sub>2</sub>]·1.45C<sub>6</sub>H<sub>6</sub>, (1·1.45C<sub>6</sub>H<sub>6</sub>), [Zr<sub>2</sub>(C<sub>7</sub>H<sub>5</sub>N<sub>4</sub>)<sub>6</sub>(C<sub>2</sub>H<sub>6</sub>N)<sub>2</sub>(C<sub>2</sub>H<sub>7</sub>N)<sub>2</sub>]·1.12C<sub>6</sub>H<sub>6</sub>·0.382CH<sub>2</sub>Cl<sub>2</sub> or [Zr<sub>2</sub>(Me<sub>2</sub>NH)<sub>2</sub>(NMe<sub>2</sub>)<sub>2</sub>(2,3-μ-Tz)<sub>3</sub>(2-η<sup>1</sup>-Tz)<sub>2</sub>(1,2-η<sup>2</sup>-Tz)]·1.12C<sub>6</sub>H<sub>6</sub>·0.38CH<sub>2</sub>Cl<sub>2</sub> (2·1.12C<sub>6</sub>H<sub>6</sub>·0.38CH<sub>2</sub>Cl<sub>2</sub>), and (C<sub>2</sub>H<sub>8</sub>N)<sub>2</sub>[Ta<sub>2</sub>(C<sub>7</sub>H<sub>5</sub>N<sub>4</sub>)<sub>8</sub>(C<sub>2</sub>H<sub>6</sub>N)<sub>2</sub>O]·0.25C<sub>7</sub>H<sub>8</sub> or (Me<sub>2</sub>NH<sub>2</sub>)<sub>2</sub>[Ta<sub>2</sub>(NMe<sub>2</sub>)<sub>2</sub>(2,3-μ-Tz)<sub>2</sub>(2-η<sup>1</sup>-Tz)<sub>6</sub>O]·0.25C<sub>7</sub>H<sub>8</sub> (3·0.25C<sub>7</sub>H<sub>8</sub>), where TzH is 5-phenyl-1H-tetrazole, have been synthesized and structurally characterized. All three complexes are dinuclear; the Ti center in 1 is six-coordinate, whereas the Zr and Ta atoms in 2 and 3 are seven-coordinate. The coordination environments of the Ti centers in 1 are similar, and so are the ligations of the Ta centers in 3. In contrast, the two Zr centers in 2 bear a different number of ligands, one of which is a bidentate η<sup>2</sup>-5-phenyltetrazolato ligand that has not been observed previously for d-block elements. The dimethylamido ligand, present in the starting materials, remained unchanged, or was converted to dimethylamine and dimethylammonium during the synthesis. Dimethylamine coordinates as a neutral ligand, whereas dimethylammonium is retained as a hydrogen-bonded entity bridging Tz ligands.

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Journal
Acta Crystallographica Section C Structural Chemistry
Published
2024-08-23
DOI
https://doi.org/10.1107/s2053229624007411
Primary Topic
Synthesis of Tetrazole Derivatives
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article
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article

Coordination variety of phenyltetrazolato and dimethylamido ligands in dimeric Ti, Zr, and Ta complexes

Ilia A. Guzei, G.A. Bikzhanova
Acta Crystallographica Section C Structural Chemistry
Synthesis of Tetrazole Derivatives
article

Coordination variety of phenyltetrazolato and dimethylamido ligands in dimeric Ti, Zr, and Ta complexes

Ilia A. Guzei, G.A. Bikzhanova
article en

Abstract

Three structurally diverse 5-phenyltetrazolato (Tz) Ti, Zr, and Ta complexes, namely, (C<sub>2</sub>H<sub>8</sub>N)[Ti<sub>2</sub>(C<sub>7</sub>H<sub>5</sub>N<sub>4</sub>)<sub>5</sub>(C<sub>2</sub>H<sub>6</sub>N)<sub>4</sub>]·1.45C<sub>6</sub>H<sub>6</sub> or (Me<sub>2</sub>NH<sub>2</sub>)[Ti<sub>2</sub>(NMe<sub>2</sub>)<sub>4</sub>(2,3-μ-Tz)<sub>3</sub>(2-η<sup>1</sup>-Tz)<sub>2</sub>]·1.45C<sub>6</sub>H<sub>6</sub>, (1·1.45C<sub>6</sub>H<sub>6</sub>), [Zr<sub>2</sub>(C<sub>7</sub>H<sub>5</sub>N<sub>4</sub>)<sub>6</sub>(C<sub>2</sub>H<sub>6</sub>N)<sub>2</sub>(C<sub>2</sub>H<sub>7</sub>N)<sub>2</sub>]·1.12C<sub>6</sub>H<sub>6</sub>·0.382CH<sub>2</sub>Cl<sub>2</sub> or [Zr<sub>2</sub>(Me<sub>2</sub>NH)<sub>2</sub>(NMe<sub>2</sub>)<sub>2</sub>(2,3-μ-Tz)<sub>3</sub>(2-η<sup>1</sup>-Tz)<sub>2</sub>(1,2-η<sup>2</sup>-Tz)]·1.12C<sub>6</sub>H<sub>6</sub>·0.38CH<sub>2</sub>Cl<sub>2</sub> (2·1.12C<sub>6</sub>H<sub>6</sub>·0.38CH<sub>2</sub>Cl<sub>2</sub>), and (C<sub>2</sub>H<sub>8</sub>N)<sub>2</sub>[Ta<sub>2</sub>(C<sub>7</sub>H<sub>5</sub>N<sub>4</sub>)<sub>8</sub>(C<sub>2</sub>H<sub>6</sub>N)<sub>2</sub>O]·0.25C<sub>7</sub>H<sub>8</sub> or (Me<sub>2</sub>NH<sub>2</sub>)<sub>2</sub>[Ta<sub>2</sub>(NMe<sub>2</sub>)<sub>2</sub>(2,3-μ-Tz)<sub>2</sub>(2-η<sup>1</sup>-Tz)<sub>6</sub>O]·0.25C<sub>7</sub>H<sub>8</sub> (3·0.25C<sub>7</sub>H<sub>8</sub>), where TzH is 5-phenyl-1H-tetrazole, have been synthesized and structurally characterized. All three complexes are dinuclear; the Ti center in 1 is six-coordinate, whereas the Zr and Ta atoms in 2 and 3 are seven-coordinate. The coordination environments of the Ti centers in 1 are similar, and so are the ligations of the Ta centers in 3. In contrast, the two Zr centers in 2 bear a different number of ligands, one of which is a bidentate η<sup>2</sup>-5-phenyltetrazolato ligand that has not been observed previously for d-block elements. The dimethylamido ligand, present in the starting materials, remained unchanged, or was converted to dimethylamine and dimethylammonium during the synthesis. Dimethylamine coordinates as a neutral ligand, whereas dimethylammonium is retained as a hydrogen-bonded entity bridging Tz ligands.

Acta Crystallographica Section C Structural ChemistryVol. 80(9)
University of Wisconsin–Madison (US)
Wayne State University, University of Wisconsin-Madison
Openalex Percentile: Top 90%
Synthesis of Tetrazole Derivatives
DOIOpen Access PDFOpenAlex
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