The synthesis and structural characterization of the first tin-bridged ansa half-sandwich complexes via a two-step protocol from Na[η(5)-C(5)H(5)Ru(CO)(2)] and in situ generated Na[η(5)-C(5)H(5)Ni(CO)] are presented. Both compounds are characterized by multinuclear NMR spectroscopy and single-crystal diffraction.

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http://dx.doi.org/10.1021/ic202512yDOI Listing

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Different Reaction Modes Operating in ansa-Half-Sandwich Magnesium Catalysts.

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April 2024

Departamento de Química, División de Ciencias Naturales y Exactas, Universidad de Guanajuato, Campus Gto, Noria Alta S/N, CP, 36050, Guanajuato, México.

Magnesium-based catalysts are becoming popular for hydroelementation reactions specially using p-block reagents. Based on the seminal report from Schäfer's group (ChemCatChem 2022, 14, e202201007), our study demonstrates that the reaction mechanisms exhibit a far greater degree of complexity than originally presumed. Magnesium has a variety of coordination modes (and access to different hybridizations) which allows this electron-deficient centre to modulate its catalytic power depending on the σ-donor properties of the reagent.

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Two ansa-half-sandwich rare-earth-metal (REM) dialkyl complexes supported by an ethylene-bridged fluorenyl (Flu)-N-heterocyclic carbene (NHC) ligand, [M{C(2)H(4)(η(5)-Flu-κ(1)-NHC)}(CH(2)SiMe(3))(2)] (M=Y, 1; Lu, 2), and a chiral ansa-sandwich samarocene incorporating a C(2) ligand, [Sm(η(5)-C(12)H(8))(2)(thf)(2)] (3), have been investigated for the coordination-addition polymerization of renewable methylene butyrolactones, α-methylene-γ-butyrolactone (MBL) and γ-methyl-α-methylene-γ-butyrolactone ((γ)MMBL). Both ansa-half-sandwich complexes 1 and 2 exhibit exceptional activity for the polymerization of (γ)MMBL at room temperature in dimethylformamide (DMF); with a 0.25 mol% catalyst loading, quantitative monomer conversion can be achieved under 1 min, giving a high turn-over frequency (TOF) of 24,000 h(-1).

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