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