Mn(I) organometallics containing the (Pr2P)-Pr-i(CH2)(2)(PPr2)-Pr-i ligand for the catalytic hydration of aromatic nitrites

The first example of a homogeneous hydration of aromatic nitrites catalyzed by manganese molecular compounds is reported. The Mn(I) organometallics fac-[(CO)(3)Mn(dippe)(Z)]X-1-n(1-n), (n = 0, 1; Z = Br, OTf, PhCN; X = OTf) were synthesized and characterized, and their reactivity was studied. The species fac-[CO)(3)Mn(dippe)(OTf)] (2) was used as a catalyst precursor for the selective hydration of benchmark benzo-nitrite (2 mol% 2, THE/H2O 1:2 v/v, 18 h, 100 degrees C) to produce benzamide in 90% isolated yield. A series of (hetero)aromatic nitrites were hydrated to synthesize the corresponding amides in very good to excellent yields (88-94%). Isotopic labeling studies accounted for a proton transfer as the rate-determining step.