The reaction of the neutral tridentate organometallic ligand trans-(CO) 3 Fe(Ph 2 Ppym) 2 with Hg 2 (ClO 4 ) 2 xH 2 O, [(cod)RhCl] 2 , (cod)PdCl 2 , PdCl 2 and Nd(SCN) 3 xH 2 O has been studied. Five new complexes were prepared and fully characterized by single-crystal X-ray analysis: [HgCl(Ph 2 Ppym) (μ-Cl)] 2 (1), space group P2 1 /n with a = 11.906(1), b = 11.263(1), c = 13.437(1) 9, β = 91.75(1)° andZ = 2; trans-[(Ph 2 Ppym) 2 Rh(CO)Cl] 0.5CH 2 Cl 2 (2), space groupC 2/c with a = 12.009(1), b = 14.536(1), c = 19.093(1) 9, β = 90.00(1)° and Z = 4; [PdCl(μ-Ph 2 Ppym)] 2 CH 2 Cl 2 (3), space groupP 2 1 /n with a = 12.295(1), b = 11.762(1), c = 23.919(1) 9, β = 90.00(1)° and Z = 4; cis-[(Ph 2 Ppym) 2 PdCl 2 ] 0.5CH 2 Cl 2 (4), space group P2 1 /n with a = 10.907(2), b = 18.525(4), c = 16.657(3) 9, β = 106.92(3)° and Z = 4; and cis-[Fe(NCS) 2 {Ph 2 P(O)pym} 2 ] (5), space groupP 2 1 /c with a = 12.747(1), b = 11.051(1), c = 25.430(1) 9 , β = 103.30(1)° and Z = 4. The results showed that (i) trans-(CO) 3 Fe(Ph 2 Ppym) 2 is a strong reductant, and (ii) the Ph 2 Ppym moiety weakly coordinates to the Fe(0) atom and can easily be transferred to another metal atom when the organoiron ligand reacts with various metal reagents.