Room temperature chemoselective hydrogenation of C[double bond, length as m-dash]C, C[double bond, length as m-dash]O and C[double bond, length as m-dash]N bonds by using a well-defined mixed donor Mn(i) pincer catalyst.

Chemoselective hydrogenation of C[double bond, length as m-dash]C, C[double bond, length as m-dash]O and C[double bond, length as m-dash]N bonds in α,β-unsaturated ketones, aldehydes and imines is accomplished at room temperature (27 °C) using a well-defined Mn(i) catalyst and 5.0 bar H 2 . Amongst the three mixed-donor Mn(i) complexes developed, κ 3 -( R2 PN 3 N Pyz )Mn(CO) 2 Br (R = Ph, i Pr, t Bu); the t Bu-substituted complex ( t Bu2 PN 3 N Pyz )Mn(CO) 2 Br shows exceptional chemoselective catalytic reduction of unsaturated bonds. This hydrogenation protocol tolerates a range of highly susceptible functionalities, such as halides (-F, -Cl, -Br, and -I), alkoxy and hydroxy, including hydrogen-sensitive moieties like acetyl, nitrile, nitro, epoxide, and unconjugated alkenyl and alkynyl groups. Additionally, the disclosed method applies to indole, pyrrole, furan, thiophene, and pyridine-containing unsaturated ketones leading to the corresponding saturated ketones. The C[double bond, length as m-dash]C bond is chemoselectively hydrogenated in α,β-unsaturated ketones, while the aldehyde's C[double bond, length as m-dash]O bond and imine's C[double bond, length as m-dash]N bond are preferentially reduced over the C[double bond, length as m-dash]C bond. A detailed mechanistic study highlighted the non-innocent behavior of the ligand in the ( t Bu2 PN 3 N Pyz )Mn(i) complex and indicated a metal-ligand cooperative catalytic pathway. The molecular hydrogen (H 2 ) acts as a hydride source, whereas MeOH provides a proton for hydrogenation. DFT energy calculations supported the facile progress of most catalytic steps, involving a crucial turnover-limiting H 2 activation.