Imidomolybdenum(IV) Porphyrin Complexes: Synthesis, Characterization, and Intermetal Imido Transfer Reactivity
Woo, L. Keith
The imido(meso-tetra-p-tolylporphyrinato)molybdenum(IV) complexes, (TTP)MoNR, where R = C6H5 (1a), p-CH3C6H4 (1b), 2,4,6-(CH3)3C6H2 (1c), and 2,6-(i-Pr)2C6H4 (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)MoNR·NC5H4-p-X, were observed. The reaction between the molybdenum imido complexes, (TTP)MoNC6H5 or (TTP)MoNC6H4CH3, and (TTP)Ti(η2-PhC⋮CPh) resulted in complete imido group transfer and two-electron redox of the metal centers to give (TTP)Mo(η2-PhC⋮CPh) and (TTP)TiNC6H5 or (TTP)TiNC6H4CH3.
Reprinted (adapted) with permission from Inorganic Chemistry 44 (2005): 7304, doi:10.1021/ic051100e. Copyright 2005 American Chemical Society.