Resonance Raman, X-ray crystallographic, and magnetic susceptibility studies of metal-metal-bonded MoRu and WOs porphyrin dimers. 1: Evidence for an unusual MO diagram
- Stanford Univ., CA (United States). Dept. of Chemistry
- Los Alamos National Lab., NM (United States)
- CEA-Grenoble (France). Dept. de Recherche Fondamentale sur la Matiere Condensee
Solution (VT NMR, Evans method magnetic susceptibility, resonance Raman) and solid-state (SQUID magnetic susceptibility, X-ray crystallography) spectroscopic studies of intertriad heterodimeric [(OEP)MoRu(OEP)] (1), [(OEP)WOs(OEP)] (2), and [(OEP)MoRu(TPP)]PF{sub 6} (3{sup +}) metalloporphyrins are reported (OEP = 2,3,7,8,12,13,17,18-octaethylporphyrinato; TPP = 5,10,15,20-tetraphenylporphyrinato). Solution and solid-state magnetic susceptibility data indicate that 1 and 2 contain two unpaired electrons in the ground electronic configuration. The presence of a {delta} bond in 3{sup +} has been confirmed by structural characterization. The experimental evidence is consistent with a molecular orbital ordering, {sigma} < {pi} < {delta} < {pi}{sup *} < {delta}{sup *}, which is different from that seen for homologous metalloporphyrin dimers with homometallic or intratriad heterometallic multiple metal-metal bonds. Resonance Raman data suggest that the heterometallic bonds are slightly stronger than isoelectronic homometallic species.
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- OSTI ID:
- 352711
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 9 Vol. 38; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
Similar Records
Heterometallic mixed triad multiple bonds in metal-porphyrin dimers
Vibrational study of multiply metal-metal bonded ruthenium porphyrin dimers