Substitution of H 2 by ligands (L) in either pure trans-[Fe(H)(η 2 -H 2 )(η 2 -dppm) 2 ] [BF 4 ], 1, or solutions of [Fe(H) 2 (dppm) 2 ] 2, L and HBF 4 .Et 2 O in which 1 is made in situ, produce the compounds trans-[Fe(H)(L)(η 2 -dppm) 2 ] [BF 4 ] (LCH 3 CN, 3; succinonitrile, 4; pyridine, 5; C 2 H 4 , 6; and N 2 , 7). The order of H 2 replacement from 1 appears to be CH 3 CN>N 2 >C 2 H 4 ∼pyridine. Evidence is presented for the protonation of the hydride ligands of 1 or 2 to produce [Fe(H 2 ) 2 (η 2 -dppm) 2 ] [BF 4 ] 2 , 8, although 8 could not be fully characterized nor could it be obtained in the solid state. Trans-[Fe(CH 3 CN) 2 (η 2 -dppm) 2 ] [BF 4 ] 2 , 9, was obtained from solutions of 8 treated with acetonitrile. The coordination geometries of 3, 9 and 4 (monodentate succinonitrile) have been confirmed by X-ray crystallography (only the gross structural features of 4 were obtained due to a poor data set from a very small crystal).