Several bisphosphine- and bisphosphite-substituted Re-imido complexes have been prepared from Re(NPh)(PPh3)2Cl3, 1, and Re(N-C6H3-i-Pr2)2Cl3(py), 4. Compound 1 reacted with trimethyl phosphate (P(OMe)3) to give a mixture of two isomers,mer,trans-Re(NPh)(P(OMe)3)2Cl3, 2, and fac,cis-Re(NPh)(P(OMe)3)2Cl3, 2a. In this reaction, the mer,trans-isomer is a major product. Complex 1 also reacted with triethylphosphine (PEt3) to exclusively give mertrans-Re(NPh)(PEt3)2Cl3, 3. Compound 4 reacted with trimethylphosphine (PMe3) to give mer,trans-Re(N-C6H3-i-Pr2)(PMe3)2Cl3, 5, which was converted to mer-Re(N-C6H3-i-Pr2)(PMe)(OPMe3)Cl3, 6, on exposure to air. Crystallographic data for 2: monoclinic space group P21/n, a = 8.870(2) Å, b = 14.393(3) Å, c = 17.114(4) Å, β = 101.43(2)°, Z = 4, R(wR2) = 0.0521(0.1293). Crystallographic data for 5: orthorhombic space group P212121, a = 11.307(l) Å, b = 11.802(l) Å, c = 19.193(2) Å, Z = 4, R(wR2) = 0.0250(0.0593). Crystallographic data for 6: orthorhombic space group P212121, a = 14.036(4) Å, b = 16.486(5) Å, c = 11.397(3) Å, Z = 4, R(wR2) = 0.0261(0.0630).