Nitrosyl derivatives of the halide-bridged complexes [M2Cp2(μ-X)(μ-PtBu2)(CO)2] (M = Mo, W
The title compounds were prepared as described previously (M = Mo, X = Cl) or by the reaction of the known unsaturated complex [W2Cp2(μ-PtBu2)(CO)4]BF4 with NaI in refluxing 1,2-dichloroethane solution. Reaction of these halide-bridged complexes with NO (1 atm) at low temperature yielded the corresp...
| Autores: | , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2024 |
| País: | España |
| Institución: | Universidad de Oviedo (UNIOVI) |
| Repositorio: | RUO. Repositorio Institucional de la Universidad de Oviedo |
| Idioma: | inglés |
| OAI Identifier: | oai:digibuo.uniovi.es:10651/75289 |
| Acceso en línea: | https://hdl.handle.net/10651/75289 https://dx.doi.org/10.1016/j.jorganchem.2024.123147 |
| Access Level: | acceso abierto |
| Sumario: | The title compounds were prepared as described previously (M = Mo, X = Cl) or by the reaction of the known unsaturated complex [W2Cp2(μ-PtBu2)(CO)4]BF4 with NaI in refluxing 1,2-dichloroethane solution. Reaction of these halide-bridged complexes with NO (1 atm) at low temperature yielded the corresponding dinitrosyl de- rivatives syn,trans-[M2Cp2X(μ-PtBu2)(CO)(NO)2], with a syn arrangement of Cp ligands relative to the M2P plane, and a transoid arrangement of the halide ligand X relative to the P atom, according to an X-ray study on the ditungsten complex (W W = 3.113(1) Å). Further decarbonylation of these products at high temperature yielded in both cases the halide-bridged complexes trans-[M2Cp2(μ-X)(μ-PtBu2)(NO)2] as major products, but the minor products were different. For the molybdenum complex, an isomer of the final product, cis-[Mo2Cp2(μ-Cl) (μ-PtBu2)(NO)2], was formed. In contrast, the minor tungsten product, anti,cis-[W2Cp2I(μ-PtBu2)(CO)(NO)2], was an isomer of the parent complex. In addition, trace amounts of the imide cyclopentadienylidene complex [W2Cp (μ-κ:η5-C5H4)I(μ-PtBu2)(NH)(NO)] was also obtained (W W = 2.9376(2) Å). Density functional theory calcula- tions were used to examine possible routes to the above dinitrosyl complexes, that seem to involve at least three reaction pathways: direct decarbonylation, rearrangement of the MCpX(NO) fragment prior to decarbonylation, and rearrangement of the MCp(CO)(NO) fragment prior to decarbonylation. |
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