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.
Inorg Chem
; 38(9): 2085-2092, 1999 May 03.
Article
em En
| MEDLINE
| ID: mdl-11670990
ABSTRACT
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(6) (3(+)) 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(+) has been confirmed by structural characterization. The experimental evidence is consistent with a molecular orbital ordering, sigma < pi < delta < pi < delta, 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.
Buscar no Google
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Inorg Chem
Ano de publicação:
1999
Tipo de documento:
Article
País de afiliação:
França