Imidomolybdenum(IV) porphyrin complexes: Synthesis, characterization, and intermetal imido transfer reactivity

The imido(meso-tetra-p-tolylporphyrinato)molybdenum(IV) complexes, (TTP)Mo=NR, where R = C6H5 (1a), p-CH3C6H4 (1b), 2A6-(CH3)(3)C6H2 (1c), and 2,6-(i-Pr)(2)C6H4 (1d), can be prepared by the reaction of (TTP)MoCl2 with 2 equiv of LiNHR in toluene. Upon treatment of the imido complexes with pyridine derivatives, NC5H4-p-X (X = CH3, CH(CH3)2, C N), new six-coordinate complexes, (TTP)Mo=NR-NC5H4-p-X, were observed. The reaction between the molybdenum imido complexes, (TTP)Mo=NC6H5 or (TTP)Mo=NC6H4CH3, and (TTP)Ti(eta(2)-PhC CPh) resulted in complete imido group transfer and two-electron redox of the metal centers to give (TTP) Mo(eta(2)-PhC CPh) and (TTP)Ti=NC6H5 or (TTP)Ti=NC6H4CH3.