American Chemical Society
om7b00243_si_001.pdf (2.18 MB)

Catalytic Hydrodefluorination of Fluoroarenes Using Ru(IMe4)2L2H2 (IMe4 = 1,3,4,5-Tetramethylimidazol-2-ylidene; L2 = (PPh3)2, dppe, dppp, dppm) Complexes

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journal contribution
posted on 2017-06-02, 20:16 authored by Mateusz K. Cybulski, Jessica E. Nicholls, John P. Lowe, Mary F. Mahon, Michael K. Whittlesey
The all-trans isomer of Ru­(IMe4)2(PPh3)2H2 (ttt-4; IMe4 = 1,3,4,5-tetramethylimidazol-2-ylidene) reacts with C6F6 at 70 °C to afford the hydride fluoride complex Ru­(IMe4)2(PPh3)2HF (ttt-6). At room temperature, ttt-6 reacts with Et3SiH to give a mixture of products, one of which is assigned as the silyl trihydride complex Ru­(IMe4)2(PPh3)­(SiEt3)­H3 (8) by comparison to the isolated and structurally characterized analogue Ru­(IMe4)2(PPh3)­(SiPh3)­H3 (9). As ttt-4 was re-formed cleanly upon heating ttt-6 with Et3SiH, it was tested in the catalytic hydrodefluorination (HDF) of C6F6 (10 mol %, 90 °C), along with 9, Ru­(IMe4)2(P-P)­HF (P-P = Ph2P­(CH2)2PPh2 (dppe, cct-13), Ph2P­(CH2)3PPh2 (dppp, cct-14), Ph2PCH2PPh2 (dppm, cct-15)), Ru­(IEt2Me2)2(PPh3)2HF (cct-7; IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene)), and Ru­(IEt2Me2)2(dppe)2HF (cct-16) for comparison. Both cct-13 and cct-14 brought about near-quantitative conversion to C6FH5 in 24 h, in comparison to ca. 50% conversion with ttt-4 in 144 h.