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Chalcogen-substituted carbenes: a density functional study of structure, stability, and donor ability† † Electronic supplementary information (ESI) available: Atomic coordinates and energies of all optimized structures (.xyz format). See DOI: https://doi.org/10.1039/d3ra03324d

ABSTRACT: Chalcogen-substituted carbenes are examined computationally using density functional theory. Several approaches are used to assess the stability and reactivity of chalcogenazol-2-ylidene carbenes (NEHCs; E = O, S, Se, Te). The known unsaturated species 1,3-dimethylimidazol-2-ylidene is studied at the same level of theory as the NEHC molecules, as a reference. Electronic structures, stability towards dimerization, and ligand properties are discussed. The results highlight the NEHCs as potentially valuable ancillary ligands for stabilizing low-valent metals or paramagnetic main group molecules. A simple, effective computational method for evaluating σ donor ability and π acidity of carbenes is presented. Chalcogen-substituted carbenes are examined computationally, highlighting their unique electronic properties and potential to stabilize radicals and low-valent metals.

SUBMITTER: Ritch J

PROVIDER: S-EPMC10240176 | biostudies-literature | 2023 Jun

REPOSITORIES: biostudies-literature

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Project description:The triphosphorus complex [Mo2Cp2(μ-η3:η3-P3)(μ-PtBu2)] was prepared in 83% yield by reacting the methyl complex [Mo2Cp2(μ-κ1:η2-CH3)(μ-PtBu2)(μ-CO)] with P4 at 333 K, a process also giving small amounts of the methyldiphosphenyl complex [Mo2Cp2(μ-η2:η2-P2Me)(μ-PtBu2)(CO)2]. The latter could be better prepared by first reacting the anionic complex Na[Mo2Cp2(μ-PtBu2)(μ-CO)2] with P4 to give the diphosphorus derivative Na[Mo2Cp2(μ-η2:η2-P2)(μ-PtBu2)(CO)2] and further reaction of the latter with MeI. Density functional theory calculations on the title complex revealed that its triphosphorus group can be viewed as an allylic-like P3- ligand acting as a six-electron donor via the external P atoms, while coordination of the internal P atom involves donation from the π orbital of the ligand and back-donation to its π* orbital, both interactions having a weakening effect on the Mo-Mo and P-P connections. The reactivity of the title compound is dominated by the electron-donor ability associated with the lone pairs located at the P atoms. Its reaction with CF3SO3Me gave [Mo2Cp2(μ-η3:η3-P3Me)(μ-PtBu2)](CF3SO3) as a result of methylation at an external atom of the P3 ligand, while its reaction with [Fe2(CO)9] enabled the addition of one, two, or three Fe(CO)4 fragments at these P atoms, but only the diiron derivative [Mo2Fe2Cp2(μ-η3:η3:κ1:κ1-P3)(μ-PtBu2)(CO)8] could be isolated. This complex bears a Fe(CO)4 fragment at each of the external atoms of the P3 ligand, and the central P atom of the latter displays the lowest 31P chemical shift reported to date (δP -721.8 ppm). The related complexes [Mo2M2Cp2(μ-η3:η3:κ1:κ1-P3)(μ-PtBu2)(CO)10] (M = Mo, W) were prepared by reacting the title compound with the corresponding [M(CO)5(THF)] complexes in toluene, while reaction with [Mo(CO)4(THF)2] also enabled the formation of the heptanuclear derivative [Mo7Cp4(μ-η3:η3:κ1:κ1-P3)2(μ-PtBu2)2(CO)14]. The interatomic distances in the above compounds indicate that the central Mo2P3 skeleton of these molecules is little modified by the attachment of 16-electron M(CO)n fragments at the external atoms of the P3 ligand.

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Chalcogen-substituted carbenes: a density functional study of structure, stability, and donor ability† † Electronic supplementary information (ESI) available: Atomic coordinates and energies of all optimized structures (.xyz format). See DOI: https://doi.org/10.1039/d3ra03324d

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