Resonance Raman, X-ray crystallographic studies of intertriad metal-metal bonds. 2: WRu and MoOs porphyrin dimers

Journal Article · Mon May 03 04:00:00 EDT 1999 · Inorganic Chemistry

DOI:https://doi.org/10.1021/ic9810337· OSTI ID:352712

Collman, J P; Harford, S T ^[1]; Franzen, S ^[1]; Shreve, A P; Woodruff, W H ^[2]

---

1. Stanford Univ., CA (United States). Dept. of Chemistry
2. Los Alamos National Lab., NM (United States)

Solution ({sup 1}H NMR, Evans method magnetic susceptibility, resonance Raman) and X-ray crystallographic spectroscopic studies of intertriad heterodimeric [(OEP)MoOs(OEP)] (3), [(OEP)WRu(OEP)] (4), [(OEP)MoOs(Tpp)]PF{sub 6} (5{sup +}), and [(OEP)WRu(TPP)]PF{sub 6} (6{sup +}) metalloporphyrins are reported (OEP = 2,3,7,8,12,13,17,18-octaethylporphyrinato; TPP = 5,10,15,20-tetraphenylporphyrinato). Evans method magnetic susceptibility data indicate that 3 and 4 contain two unpaired electrons in the ground electronic configuration. Resonance Raman spectra of 3, 4, 5{sup +}, and 6{sup +} suggest that WRu bonds are 5--10% stronger than corresponding MoOs species. Structural characterization of 5{sup +} and 6{sup +} demonstrates metal-metal bond lengths of 2.30 (WRu) and 2.24 (MoOs) {angstrom}, respectively. The possibility of a special stability associated with polar heterometallic multiple bonds is discussed.

• Sponsoring Organization: USDOE, Washington, DC (United States)
• OSTI ID: 352712
• 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

Related Subjects

36 MATERIALS SCIENCE
CHEMICAL BONDS
ELECTRONIC STRUCTURE
MAGNETIC SUSCEPTIBILITY
MOLYBDENUM COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OSMIUM COMPOUNDS
PORPHYRINS
RUTHENIUM COMPOUNDS
TUNGSTEN COMPOUNDS