Synthesis and Characterization of Di‐ and Tricarbonylhydridomanganese(I) Complexes

Hydrido complexes [MnH(CO) 3 L 1–3 ] [L 1 = 1,2‐bis‐(diphenylphosphanoxy)‐ethane ( 1 ); L 2 = 1,2‐bis‐(diisopropylphosphanoxy)ethane ( 2 ); L 3 = 1,3‐bis‐(diphenylphosphanoxy)‐propane ( 3 )] were prepared by treating [MnH(CO) 5 ] with the appropriate bidentate ligand by heating to reflux. Photoirradiation of a toluene solution of complexes 1 and 2 in the presence of PPh n (OR) 3– n ( n = 0, 1; R = Me, Et) leads to the replacement of a CO ligand by the corresponding monodentate phosphite or phosphonite ligand to give new hydrido compounds of formula [MnH(CO) 2 (L 1–2 )(L)] [L = P(OMe) 3 ( 1a – 2a ); P(OEt) 3 ( 1b – 2b ); PPh(OMe) 2 ( 1c – 2c ); PPh(OEt) 2 ( 1d – 2d )]. All complexes were characterized by IR, 1 H, 13 C and 31 P NMR spectroscopy. In case of compounds 2 and 3 , suitable crystals for X‐ray diffraction studies were isolated.