Selective Transfer Semihydrogenation of Alkynes Catalyzed by an Iron PCP Pincer Alkyl Complex.

Two bench-stable Fe(II) alkyl complexes [Fe(κPCP-PCP-Pr)(CO)(R)] (R = CHCHCH, CH) were obtained by the treatment of [Fe(κPCP-PCP-Pr)(CO)(H)] with NaNH and subsequent addition of CHCHCHBr and CHI, respectively. The reaction proceeds via the anionic Fe(0) intermediate Na[Fe(κPCP-PCP-Pr)(CO)]. The catalytic performance of both alkyl complexes was investigated for the transfer hydrogenation of terminal and internal alkynes utilizing PhSiH and PrOH as a hydrogen source. Precatalyst activation is initiated by migration of the alkyl ligand to the carbonyl C atom of an adjacent CO ligand. In agreement with previous findings, the rate of alkyl migration follows the order Pr > Me. Accordingly, [Fe(κPCP-PCP-Pr)(CO)(CHCHCH)] is the more active catalyst. The reaction takes place at 25 °C with a catalyst loading of 0.5 mol%. There was no overhydrogenation, and in the case of internal alkynes, exclusively, -alkenes are formed. The implemented protocol tolerates a variety of electron-donating and electron-withdrawing functional groups including halides, nitriles, unprotected amines, and heterocycles. Mechanistic investigations including deuterium labeling studies and DFT calculations were undertaken to provide a reasonable reaction mechanism.