Low-Dimensional Architectures in Isomeric <i>cis</i>-PtCl<sub>2</sub>{Ph<sub>2</sub>PCH<sub>2</sub>N(Ar)CH<sub>2</sub>PPh<sub>2</sub>} Complexes Using Regioselective-N(Aryl)-Group Manipulation
The solid-state behaviour of two series of isomeric, phenol-substituted, aminomethylphosphines, as the free ligands and bound to Pt<sup>II</sup>, have been extensively studied using single crystal X-ray crystallography. In the first library, isomeric diphosphines of the type Ph<sub>...
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| Autores principales: | , , , |
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| Formato: | article |
| Lenguaje: | EN |
| Publicado: |
MDPI AG
2021
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| Materias: | |
| Acceso en línea: | https://doaj.org/article/121a97a7c71d47f38ce993cbb44ea037 |
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| Sumario: | The solid-state behaviour of two series of isomeric, phenol-substituted, aminomethylphosphines, as the free ligands and bound to Pt<sup>II</sup>, have been extensively studied using single crystal X-ray crystallography. In the first library, isomeric diphosphines of the type Ph<sub>2</sub>PCH<sub>2</sub>N(Ar)CH<sub>2</sub>PPh<sub>2</sub> [<b>1a</b>–<b>e</b>; Ar = C<sub>6</sub>H<sub>3</sub>(Me)(OH)] and, in the second library, amide-functionalised, isomeric ligands Ph<sub>2</sub>PCH<sub>2</sub>N{CH<sub>2</sub>C(O)NH(Ar)}CH<sub>2</sub>PPh<sub>2</sub> [<b>2a</b>–<b>e</b>; Ar = C<sub>6</sub>H<sub>3</sub>(Me)(OH)], were synthesised by reaction of Ph<sub>2</sub>PCH<sub>2</sub>OH and the appropriate amine in CH<sub>3</sub>OH, and isolated as colourless solids or oils in good yield. The non-methyl, substituted diphosphines Ph<sub>2</sub>PCH<sub>2</sub>N{CH<sub>2</sub>C(O)NH(Ar)}CH<sub>2</sub>PPh<sub>2</sub> [<b>2f</b>, Ar = 3-C<sub>6</sub>H<sub>4</sub>(OH); <b>2g</b>, Ar = 4-C<sub>6</sub>H<sub>4</sub>(OH)] and Ph<sub>2</sub>PCH<sub>2</sub>N(Ar)CH<sub>2</sub>PPh<sub>2</sub> [<b>3</b>, Ar = 3-C<sub>6</sub>H<sub>4</sub>(OH)] were also prepared for comparative purposes. Reactions of <b>1a</b>–<b>e</b>, <b>2a</b>–<b>g</b>, or <b>3</b> with PtCl<sub>2</sub>(η<sup>4</sup>-cod) afforded the corresponding square-planar complexes <b>4a</b>–<b>e</b>, <b>5a</b>–<b>g</b>, and <b>6</b> in good to high isolated yields. All new compounds were characterised using a range of spectroscopic (<sup>1</sup>H, <sup>31</sup>P{<sup>1</sup>H}, FT–IR) and analytical techniques. Single crystal X-ray structures have been determined for <b>1a</b>, <b>1b</b>∙CH<sub>3</sub>OH, <b>2f</b>∙CH<sub>3</sub>OH, <b>2g</b>, <b>3</b>, <b>4b</b>∙(CH<sub>3</sub>)<sub>2</sub>SO, <b>4c</b>∙CHCl<sub>3</sub>, <b>4d</b>∙½Et<sub>2</sub>O, <b>4e</b>∙½CHCl<sub>3</sub>∙½CH<sub>3</sub>OH, <b>5a</b>∙½Et<sub>2</sub>O, <b>5b</b>, <b>5c</b>∙¼H<sub>2</sub>O, <b>5d</b>∙Et<sub>2</sub>O, and <b>6</b>∙(CH<sub>3</sub>)<sub>2</sub>SO. The free phenolic group in <b>1b</b>∙CH<sub>3</sub>OH, <b>2f</b>∙CH<sub>3</sub>OH<sub>,</sub><b>2g</b>, <b>4b</b>∙(CH<sub>3</sub>)<sub>2</sub>SO, <b>5a</b>∙½Et<sub>2</sub>O, <b>5c</b>∙¼H<sub>2</sub>O, and <b>6</b>∙(CH<sub>3</sub>)<sub>2</sub>SO exhibits various intra- or intermolecular O–H∙∙∙X (X = O, N, P, Cl) hydrogen contacts leading to different packing arrangements. |
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