Ruthenium complexes with a terminal hydrazido ligand. Synthesis, spectroscopy, and X-ray crystal structure

X R Sun; J S Huang; K K Cheung; C M Che

doi:10.1021/ic990467e

Ruthenium complexes with a terminal hydrazido ligand. Synthesis, spectroscopy, and X-ray crystal structure

Inorg Chem. 2000 Feb 21;39(4):820-6. doi: 10.1021/ic990467e.

Authors

X R Sun¹, J S Huang, K K Cheung, C M Che

Affiliation

¹ Department of Chemistry and the PKU-HKU Joint Laboratory on Rare Earth Materials and Bioinorganic Chemistry, The University of Hong Kong, Hong Kong.

PMID: 11272583
DOI: 10.1021/ic990467e

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.