{"title":"二聚钛、锆和钽配合物中苯基四唑和二甲基氨基配体的配位变化。","authors":"Galina A Bikzhanova, Ilia A Guzei","doi":"10.1107/S2053229624007411","DOIUrl":null,"url":null,"abstract":"<p><p>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.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":0.7000,"publicationDate":"2024-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11371001/pdf/","citationCount":"0","resultStr":"{\"title\":\"Coordination variety of phenyltetrazolato and dimethylamido ligands in dimeric Ti, Zr, and Ta complexes.\",\"authors\":\"Galina A Bikzhanova, Ilia A Guzei\",\"doi\":\"10.1107/S2053229624007411\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>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.</p>\",\"PeriodicalId\":7115,\"journal\":{\"name\":\"Acta Crystallographica Section C Structural Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":0.7000,\"publicationDate\":\"2024-09-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11371001/pdf/\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Acta Crystallographica Section C Structural Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1107/S2053229624007411\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2024/8/23 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Acta Crystallographica Section C Structural Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1107/S2053229624007411","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/8/23 0:00:00","PubModel":"Epub","JCR":"Q4","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
摘要
三种结构不同的 5-苯基四氮唑（Tz）Ti、Zr 和 Ta 复合物，即 (C2H8N)[Ti2(C7H5N4)5(C2H6N)4]-1.45C6H6 或 (Me2NH2)[Ti2(NMe2)4(2,3-μ-Tz)3(2-η1-Tz)2]-1.45C6H645C6H6, (1·1.45C6H6), [Zr2(C7H5N4)6(C2H6N)2(C2H7N)2]·1.12C6H6·0.382CH2Cl2 or [Zr2(Me2NH)2(NMe2)2(2,3-μ-Tz)3(2-η1-Tz)2(1,2-η2-Tz)]·1.12C6H6-0.38CH2Cl2 (2-1.12C6H6-0.38CH2Cl2)，以及 (C2H8N)2[Ta2(C7H5N4)8(C2H6N)2O]-0.25C7H8 或 (Me2NH2)2[Ta2(NMe2)2(2,3-μ-Tz)2(2-η1-Tz)6O]-0.25C7H8 (3-0.25C7H8)，其中 TzH 是 5-苯基-1H-四氮唑。这三种配合物都是双核的；1 中的 Ti 中心是六配位的，而 2 和 3 中的 Zr 和 Ta 原子是七配位的。相比之下，2 中的两个 Zr 中心具有不同数量的配体，其中一个是双性 η2-5-苯基四唑配体，这是以前从未在 d 块元素中观察到的。起始材料中的二甲基氨基配体保持不变，或在合成过程中转化为二甲基胺和二甲基铵。二甲基胺作为中性配体配位，而二甲基铵则作为桥接 Tz 配体的氢键实体保留下来。
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, (C2H8N)[Ti2(C7H5N4)5(C2H6N)4]·1.45C6H6 or (Me2NH2)[Ti2(NMe2)4(2,3-μ-Tz)3(2-η1-Tz)2]·1.45C6H6, (1·1.45C6H6), [Zr2(C7H5N4)6(C2H6N)2(C2H7N)2]·1.12C6H6·0.382CH2Cl2 or [Zr2(Me2NH)2(NMe2)2(2,3-μ-Tz)3(2-η1-Tz)2(1,2-η2-Tz)]·1.12C6H6·0.38CH2Cl2 (2·1.12C6H6·0.38CH2Cl2), and (C2H8N)2[Ta2(C7H5N4)8(C2H6N)2O]·0.25C7H8 or (Me2NH2)2[Ta2(NMe2)2(2,3-μ-Tz)2(2-η1-Tz)6O]·0.25C7H8 (3·0.25C7H8), 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 η2-5-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.
期刊介绍：
Acta Crystallographica Section C: Structural Chemistry is continuing its transition to a journal that publishes exciting science with structural content, in particular, important results relating to the chemical sciences. Section C is the journal of choice for the rapid publication of articles that highlight interesting research facilitated by the determination, calculation or analysis of structures of any type, other than macromolecular structures. Articles that emphasize the science and the outcomes that were enabled by the study are particularly welcomed. Authors are encouraged to include mainstream science in their papers, thereby producing manuscripts that are substantial scientific well-rounded contributions that appeal to a broad community of readers and increase the profile of the authors.
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