Preparation, Characterization, and Catalytic Reactions of NCN Pincer Iron Complexes Containing Stannyl, Silyl, Methyl, and Phenyl Ligands

Preparation and reactivity of chiral and achiral NCN pincer Fe complexes containing bis­(oxazolinyl)­phenyl (abbreviated as phebox) ligands with SnMe₃, SiMe₃, Me, and Ph ligands were investigated. Irradiation of (phebox)­SnMe₃ (2) with 1 equiv of Fe­(CO)₅ led to oxidative addition to give NCN pincer stannyl complex (phebox)­Fe­(CO)₂(SnMe₃) (3). Similarly, oxidative addition of (phebox)­SiMe₃ (4) with Fe­(CO)₅ resulted in the formation of silyl complex (phebox)­Fe­(CO)₂SiMe₃ (5). Me and Ph complexes (phebox)­Fe­(CO)₂R (7, R = Me; 8, R = Ph) were synthesized by transmetalation of the bromide complex (phebox)­Fe­(CO)₂Br (1) with ZnMe₂ and ZnPh₂, respectively. These phebox Fe complexes served as catalysts for hydrosilylation of a ketone and C–H silylation of N-methylindole.