Mono(η
            <sup>5</sup>
            ‐Pentamethylcyclopentadienyl) Complexes of Osmium

Gross, Christopher L.; Brumaghim, Julia L.; Jefferis, Jesse M.; Dickinson, Paul W.; Girolami, Gregory S.; Gribble, Christopher W.; Tilley, T. Don

doi:10.1002/9781118744994.ch15

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References 16 publications

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“…The osmium methyl complex (C 5 Me 5 )Os(dfmpm)(CH 3 ) was prepared (see the Supplementary Materials) in 54% overall yield in two steps from (C 5 Me 5 ) 2 Os 2 Br 4 (Fig. 1) ( 41 , 42 ); the second step, alkylation of (C 5 Me 5 )Os(dfmpm)Br, required the use of dimethylzinc because methyllithium and methylmagnesium reagents deprotonate the CH 2 group in the backbone of the dfmpm ligand, and trimethylaluminum activates the C─F bonds of the phosphine. The Os-CH 3 resonance in the 1 H NMR spectrum is a triplet ( J HP = 7.5 Hz) of septets ( J HF = 2 Hz); the septet splitting shows that there is a remarkably strong five-bond coupling between the methyl protons and 6 of the 12 fluorine atoms of the dfmpm ligand.…”

Section: Resultsmentioning

confidence: 99%

An osmium(II) methane complex: Elucidation of the methane coordination mode

et al. 2023

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The activation of inert C─H bonds by transition metals is of considerable industrial and academic interest, but important gaps remain in our understanding of this reaction. We report the first experimental determination of the structure of the simplest hydrocarbon, methane, when bound as a ligand to a homogenous transition metal species. We find that methane binds to the metal center in this system through a single M···H-C bridge; changes in the 1 J CH coupling constants indicate clearly that the structure of the methane ligand is significantly perturbed relative to the free molecule. These results are relevant to the development of better C─H functionalization catalysts.

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Section: Resultsmentioning

confidence: 99%