Cu(I) and Ag(I) complexes of two sterically demanding Xylyl-Substituted phosphine Ligands: Synthesis, Characterization, and structural examination
Two sterically demanding tertiary phosphines, PiPr2Xyl and PtBu2Xyl, (Xyl = 2,6-dimethylphenyl), the latter reported here for the first time, have been used to synthesize a series of dinuclear complexes of the general formula [M(μ-X)PR2Xyl]2, (R = iPr, tBu; M = Cu: X = Cl, Br, I, OTf; M = Ag: X = OT...
| Autores: | , , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2023 |
| País: | España |
| Institución: | Universidad de Sevilla (US) |
| Repositorio: | idUS. Depósito de Investigación de la Universidad de Sevilla |
| OAI Identifier: | oai:idus.us.es:11441/157265 |
| Acceso en línea: | https://hdl.handle.net/11441/157265 https://doi.org/10.1016/j.ica.2023.121623 |
| Access Level: | acceso abierto |
| Palabra clave: | 31P NMR Coordination Chemistry Group 11 metal complexes Phosphine ligands Sterically demanding ligands X-ray structures |
| Sumario: | Two sterically demanding tertiary phosphines, PiPr2Xyl and PtBu2Xyl, (Xyl = 2,6-dimethylphenyl), the latter reported here for the first time, have been used to synthesize a series of dinuclear complexes of the general formula [M(μ-X)PR2Xyl]2, (R = iPr, tBu; M = Cu: X = Cl, Br, I, OTf; M = Ag: X = OTf, NTf2). All compounds have been characterized by multinuclear NMR spectroscopy in solution and, with the exception of AgNTf2(PtBu2Xyl), by X-ray diffraction analyses. The doubly halido-bridged compounds [Cu(μ-X)PR2Xyl]2 (R = iPr, tBu; X = Cl, Br, I) display Ci, C2-like, or C1 molecular symmetry, depending on the anion and the R group, and enclose planar or disphenoidal [CuX]2 cores with short, bonding Cu—Cu distances in case of X = I. On the other hand, centrosymmetric 8-membered rings with twist-chair conformations are found in the solid state structures of [M(μ-OTf)PR2Xyl]2 (R = iPr, tBu; M = Cu, Ag) and [Ag(μ-NTf2)PiPr2Xyl]2, with the anions in a κ2-μ2 coordination mode. Additionally, the cationic complex [Cu(PR2Xyl)2]+ has been obtained as a triflate or BArF salt (BArF- = B{3,5-(CF3)2C6H3}4-), and shows C2-like symmetry in the solid state, with PCuP angles of ca. 168-169° and synclinal dispositions of the Xyl groups with respect to the P∙∙∙P axis. Comparative discussion of relevant NMR data of Cu(I), Ag(I), and Au(I) adducts of the title phosphines is also provided. |
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