Abstract
The equilibria between Ln(fod)3 (Ln = Pr, Eu, Ho, or Yb; fod = 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyloctanedionate) and the basic substrate (π-C5H5)Fe(CO)2(CN) have been studied by vapor pressure osmometry on benzene solutions. Dimers and, in some cases, higher aggregates of the shift reagents are found in pure Ln(fod)3 solutions. In general, the shift reagent : substrate systems form 1:1 and 1:2 complexes. In the case of Pr(fod)3 1:3 complex formation is also observed. The relative successive formation constants for 1:2 adduct formation decrease from light to heavy lanthanide. This, as well as the 1:3 formation with Pr(fod)3, is thought to reflect greater steric crowding with the heavier members. The osmometry results are compared with nmr shifts determined under similar conditions, and the factors determining the shapes of plots of substrate shift vs. shift reagent to substrate ratio are discussed.
| Original language | English |
|---|---|
| Pages (from-to) | 3548-3552 |
| Number of pages | 5 |
| Journal | Journal of the American Chemical Society |
| Volume | 95 |
| Issue number | 11 |
| Publication status | Published - 1973 |
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ASJC Scopus subject areas
- Chemistry(all)
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Delineation of shift reagent-substrate equilibria. / Porter, R.; Marks, Tobin J; Shriver, D. F.
In: Journal of the American Chemical Society, Vol. 95, No. 11, 1973, p. 3548-3552.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Delineation of shift reagent-substrate equilibria
AU - Porter, R.
AU - Marks, Tobin J
AU - Shriver, D. F.
PY - 1973
Y1 - 1973
N2 - The equilibria between Ln(fod)3 (Ln = Pr, Eu, Ho, or Yb; fod = 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyloctanedionate) and the basic substrate (π-C5H5)Fe(CO)2(CN) have been studied by vapor pressure osmometry on benzene solutions. Dimers and, in some cases, higher aggregates of the shift reagents are found in pure Ln(fod)3 solutions. In general, the shift reagent : substrate systems form 1:1 and 1:2 complexes. In the case of Pr(fod)3 1:3 complex formation is also observed. The relative successive formation constants for 1:2 adduct formation decrease from light to heavy lanthanide. This, as well as the 1:3 formation with Pr(fod)3, is thought to reflect greater steric crowding with the heavier members. The osmometry results are compared with nmr shifts determined under similar conditions, and the factors determining the shapes of plots of substrate shift vs. shift reagent to substrate ratio are discussed.
AB - The equilibria between Ln(fod)3 (Ln = Pr, Eu, Ho, or Yb; fod = 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyloctanedionate) and the basic substrate (π-C5H5)Fe(CO)2(CN) have been studied by vapor pressure osmometry on benzene solutions. Dimers and, in some cases, higher aggregates of the shift reagents are found in pure Ln(fod)3 solutions. In general, the shift reagent : substrate systems form 1:1 and 1:2 complexes. In the case of Pr(fod)3 1:3 complex formation is also observed. The relative successive formation constants for 1:2 adduct formation decrease from light to heavy lanthanide. This, as well as the 1:3 formation with Pr(fod)3, is thought to reflect greater steric crowding with the heavier members. The osmometry results are compared with nmr shifts determined under similar conditions, and the factors determining the shapes of plots of substrate shift vs. shift reagent to substrate ratio are discussed.
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M3 - Article
VL - 95
SP - 3548
EP - 3552
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 11
ER -