Functionalization of Carbon Dioxide with Ethylene at Molybdenum Hydride Complexes
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https://figshare.com/articles/dataset/Functionalization_of_Carbon_Dioxide_with_Ethylene_at_Molybdenum_Hydride_Complexes/2394292
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资源简介：
The molybdenum tetrahydride species
(Triphos)MoH4PPh3 (Triphos = PhP(CH2CH2PPh2)2) generated from sodium
triethylborohydride addition
to (Triphos)MoCl3 was found to promote CO2 functionalization
to afford acrylate, propionate, and formate species. The formation
of (Triphos)MoH4PPh3 occurs via a (Triphos)Mo(H)Cl(PPh3) intermediate followed by dismutation of an unobserved six-coordinate
molybdenum(II) dihydride complex. Addition of dihydrogen to the dismuation
product mixture affords a nearly quantitative yield of (Triphos)MoH4PPh3. The molybdenum tetrahydride species facilitates
CO2 insertion into a metal hydride to produce a formate
complex, (Triphos)Mo(H)(κ2-CHO2)(PPh3), with an observed rate constant of [2.9(2)] × 10–4 s–1 (25 °C), which is independent
of CO2 pressure. Selective formation of acrylate and propionate
carbon dioxide–ethylene coupling products, (Triphos)Mo(H)(κ2-C3H3O2)(PPh3)
and (Triphos)Mo(H)(κ2-C3H5O2)(PPh3), was achieved by sequential addition of
olefin and heterocumulene to (Triphos)MoH4PPh3. A formally zerovalent TriphosMo(η2-C2H4)3 intermediate was characterized by NMR
spectroscopy and computational analysis along the pathway for carbon
dioxide–ethylene coupling.
创建时间：
2016-02-19
