N[sbnd]o bond cleavage and n2 activation reactions of the nitrosyl-bridged complex [mo2cp2(µ-ptbu2)(µ-no)(no)2]
The title compound was prepared through a three-step procedure starting with the hydride complex [Mo2Cp2(µH)(µ-Pt Bu2)(CO)4], which was first dehydrogenated through reaction with HBF4⋅OEt2 to give the unsaturated complex [Mo2Cp2(µ-Pt Bu2)(CO)4](BF4) (Mo=Mo), which displays a transoid structure accor...
| 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:10651/76925 |
| Acceso en línea: | https://hdl.handle.net/10651/76925 https://dx.doi.org/10.1016/j.jorganchem.2024.123375 |
| Access Level: | acceso abierto |
| Sumario: | The title compound was prepared through a three-step procedure starting with the hydride complex [Mo2Cp2(µH)(µ-Pt Bu2)(CO)4], which was first dehydrogenated through reaction with HBF4⋅OEt2 to give the unsaturated complex [Mo2Cp2(µ-Pt Bu2)(CO)4](BF4) (Mo=Mo), which displays a transoid structure according to experimental (Mo-Mo = 2.8283(7) Å) and Density Functional Theory studies. The latter was then reacted with NO to give the dinitrosyl derivative [Mo2Cp2(µ-Pt Bu2)(CO)2(NO)2](BF4), which in turn was further decarbonylated and nitrosylated upon reaction with [N(PPh3)2]NO2 to give the title nitrosyl-bridged complex (Mo-Mo = 2.905(1) Å). This complex displayed a structure comparable to that of its PCy2-bridged analogue, with similar pyramidalization of the bridging nitrosyl, but a more pronounced folding of the central MoPMoN skeleton and bending of terminal nitrosyls. It also displayed a similar N–O bond activation chemistry, as shown by its reactions with HBF4⋅OEt2 to give the nitroxyl-bridged complex [Mo2Cp2(µ-Pt Bu2)(µ-k1 :η2 -HNO)(NO)2](BF4) (HN–O = 1.330(8) Å), with P (OEt)3 to give the phosphoraniminate-bridged complex [Mo2Cp2(µ-Pt Bu2){µ-NP(OEt)3}(NO)2], and with Na(Hg) to give the amide-bridged derivative [Mo2Cp2(µ-Pt Bu2)(µ-NH2)(NO)2]. Under a nitrogen atmosphere, however, the latter reaction also gave a minor side product identified as the dinitrogen-bridged derivative [Mo4Cp4(µPt Bu2)2(µ4-N2)(NO)4]. This tetranuclear complex displays a dinitrogen molecule bridging four metal atoms in the novel µ4-k1 :k1 :k1 :k1 coordination mode, with strong metal-nitrogen interactions taking the N2 ligand to the diazendiide (N2 2-) limit (N–N = 1.241(3) Å). |
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