Reactions of the Technetium(I) Carbonyl Complexes [Tc(PMe2Ph)3(CO)2Cl] and [Tc(PPh3)2(CO)3Cl] toward Pseudoallyl Ligands Such as Triazenido, Formamidinato, and Acetamidinato. Crystal Structures of [Tc(PMe2Ph)2(CO)2(p-CH3C6H4N-N-NC6H4CH3-p)] and [Tc(PMe2Ph)2(CO)2(C6H5N-C(CH3)-NC6H5)]

New technetium(I) complexes of bidentate pseudoallyl ligands as triazenido, formamidinato, and acetamidinato have been synthesized and characterized. X-ray structure determinations of [Tc(PMe2Ph)2(CO)2(p-CH3C6H4N-N-NC6H4CH3-p)] (1a) and [Tc(PMe2Ph)2(CO)2(C6H5N-C(CH3)-NC6H5)] (1c) show the technetium atom in a distorted octahedral coordination geometry with two axial PMe2Ph and two cis-CO groups and the chelate ligands, which form a four-membered ring with the metal. Compound la crystallizes in space group Pbca of the orthorhombic system with a = 11.036 (2) Å, b = 14.657 (4) Å, c = 38.92 (1) Å, and R = 0.045 for 3381 diffractometer data with I ≥3σ(I). Compound 1c crystallizes in the same space group, Pbca, with a = 8.954 (3) Å, b = 16.727 (2) Å, c = 41.435 (5) Å, and R = 0.035 for 4108 diffractometer data with I ≥ 3σ(I). © 1985, American Chemical Society. All rights reserved.