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

Journal Article · · Inorganic Chemistry
DOI:https://doi.org/10.1021/ic9810337· OSTI ID:352712
;  [1];  [1]; ;  [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