Abstract
The carbonyl complex of (meso-tetraphenyltetrabenzoporphyrinato)ruthenium(II), Ru(TPTBP)(CO), has been synthesized and characterized by FABMS, UV/vis, 1H NMR, and IR spectroscopy. Six-coordinate complexes Ru(TPTBP)(CO)(L) with different π-bonding-capability ligands (L = NEt3, pip, 1-MeIm, py, PBu3) coordinated trans to CO have been studied. The shifts in νCO for this series of complexes are consistent with the existence of M → CO π-back-bonding. In contrast to what would be expected by nitrogen basicity, νCO values for Ru(TPTBP)(CO), Ru(TPP)(CO), and Ru(OEP)(CO) are 1959, 1930, and 1917 cm-1, respectively. This result suggests that TPTBP should be both a better σ-donor and a better π-acceptor than normal porphyrin systems (P). Oxidation studies of Ru(TPTBP)(CO), Ru(TPTBP)(CO)(py), and Ru(TPTBP)(py)2 have been carried out both electrochemically and chemically. 1H NMR, ESR, and electronic spectroscopic studies suggest that there are two different types of oxidation products. The sites of oxidation should bo...
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