The photochemical reactions of the “piano stool” complexes CpMn(CO)3, CpRe(CO)3, and Cp* Mn(CO)3(Cp* = η5-C5Me5) with the bidentate halophosphine ligand 1,2-bis(dichlorophosphino)ethane, Cl2PCH2CH2PCl2(dcpe), gave the chelate complexes CpMn(CO)dcpe (1), CpRe(CO)dcpe (2), and Cp* Mn(CO)dcpe (3), respectively. Reactions of the dihalophosphine complexes1,2with excess F1-and MeO1-gave the substituted compounds CpM(CO)(R2PCH2CH2PR2) (4, M = Mn, R = F;5, M = Mn, R = MeO;6, M = Re, R = F). The ligand-bridged bimetallic complexes [CpM(CO)2](μ-dcpe)[(CO)2M′Cp] (9, M,M′ = Mn;10, M,M′ = Re;11, M = Mn, M′ = Re) were prepared by treatment of the dangling compounds CpM(CO)2dcpe (7, M = Mn;8, M = Re) with the solvento complex CpM′(CO)2(THF) (M′ = Mn or Re). The crystal structures of1, 2, and6were determined by single crystal X-ray structure analyses.1: monoclinic, P21/c, a = 12.008(2) Å, b = 15.685(2) Å, c = 14.980(2) Å,β= 91.01(2)°, V = 2821.0(6) Å3, Z = 8, R = 0.046;2: monoclinic, P21/c, a = 12.551(2) Å,β= 8.786(2) Å, c = 12.998(2) Å,β= 92.71(2)°, V = 1431.8(4) Å3, Z = 4, R = 0.040;6: triclinic, P1, a = 6.604(2) Å, b = 8.790(2) Å, c = 11.007(2) Å,α= 87.81(2)°,β= 75.48(2)°,γ= 68.27(2)°, V = 573.54(6) Å3, Z = 2, R = 0.038.