C≡n and n≡o bond cleavages of acetonitrile and nitrosyl ligands at a dimolybdenum center to render ethylidyne and acetamidinate ligands

Extended reduction of [Mo2Cp2(μ-Cl)(μ-PtBu2)(NO)2] (1) with Na(Hg) in acetonitrile (MeCN) at room temperature resulted in an unprecedented full cleavage of the C≡N bond of a coordinated MeCN molecule to yield the vinylidene derivative Na[Mo2Cp2(μ-PtBu2)(μ-CCH2)(NO)2], which upon protonation with (NH...

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Detalles Bibliográficos
Autores: Álvarez Fidalgo, María Ángeles|||0000-0002-3313-1467, García Díaz, María Esther|||0000-0002-9185-0099, García Vivó, Daniel|||0000-0002-2441-2486, Guerra Muñiz, Ana María, Ruiz Álvarez, Miguel Ángel|||0000-0002-9016-4046
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:10651/73253
Acceso en línea:https://hdl.handle.net/10651/73253
https://dx.doi.org/10.1021/acs.inorgchem.3c03697
Access Level:acceso abierto
Descripción
Sumario:Extended reduction of [Mo2Cp2(μ-Cl)(μ-PtBu2)(NO)2] (1) with Na(Hg) in acetonitrile (MeCN) at room temperature resulted in an unprecedented full cleavage of the C≡N bond of a coordinated MeCN molecule to yield the vinylidene derivative Na[Mo2Cp2(μ-PtBu2)(μ-CCH2)(NO)2], which upon protonation with (NH4)PF6 gave the ethylidyne complex [Mo2Cp2(μ-PtBu2)(μ-CMe)(NO)2] [Mo1–Mo2 = 2.9218(2) Å] in a selective and reversible way. Controlled reduction of 1 at 273 K yielded instead, after protonation, the 30-electron acetamidinate complex [Mo2Cp2(μ-PtBu2)(μ-κN:κN′-HNCMeNH)(μ-NO)]PF6 [Mo1–Mo2 = 2.603(2) Å], in a process thought to stem from the paramagnetic MeCN-bridged intermediate [Mo2Cp2(μ-PtBu2)(μ-NCMe)(NO)2], followed by a complex sequence of elementary steps including cleavage of the N≡O bond of a nitrosyl ligand.

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