Electronic Structure and Donor Ability of an Unsaturated Triphosphorus-Bridged Dimolybdenum Complex
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https://figshare.com/articles/dataset/Electronic_Structure_and_Donor_Ability_of_an_Unsaturated_Triphosphorus-Bridged_Dimolybdenum_Complex/15016554
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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.
创建时间：
2021-07-19
