Ruthenium complexes with a terminal hydrazido ligand. Synthesis, spectroscopy, and X-ray crystal structure |
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| Authors: | Sun X R Huang J S Cheung K K Che C M |
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| Institution: | Department of Chemistry and the PKU-HKU Joint Laboratory on Rare Earth Materials and Bioinorganic Chemistry, The University of Hong Kong, Hong Kong. |
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| Abstract: | Bis(1,1-diphenylhydrazido(1-))ruthenium(IV) porphyrins, Ru(IV)(Por)(NHNPh2)2] (Por = TPP, TTP, 4-Cl-TPP, 4-MeO-TPP), were prepared in approximately 60% yields through the reaction of dioxoruthenium(VI) porphyrins, Ru(VI)(Por)O2], with 1,1-diphenylhydrazine in ethanol. This new type of ruthenium complex has been characterized by 1H NMR, IR, UV-vis, and FABMS with elemental analysis. The crystal structure of Ru(IV)(TTP)(NHNPh2)2], which reveals an eta1-coordination mode for both hydrazido axial ligands, has been determined. The average Ru-NHNPh2 distance and Ru-N-N angle were found to be 1.911(3) A and 141.1(3) degrees, respectively. The porphyrin ring exhibits a ruffling distortion that is unprecedentedly large for ruthenium complexes with simple porphyrinato ligands (such as TTP). This is probably due to the steric effect of the axial hydrazido(1-) ligands. |
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