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Title: A Scandium-Stabilized Diisophosphaethynolate Ligand: [OCPPCO] 4−

Authors:
ORCiD logo [1];  [2];  [1];  [3]; ORCiD logo [1]
  1. Department of Chemistry, University of Pennsylvania, Philadelphia PA 19104 USA
  2. Department of General Chemistry, Vrije Universiteit Brussel, Pleinlaan 2 1050 Brussels Belgium
  3. Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog Weg 1, Hönggerberg 8093 Zürich Switzerland
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1414598
Grant/Contract Number:
DEFG02-07ER15893
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Angewandte Chemie
Additional Journal Information:
Journal Volume: 130; Journal Issue: 4; Related Information: CHORUS Timestamp: 2018-01-16 11:16:36; Journal ID: ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Grant, Lauren N., Pinter, Balazs, Manor, Brian C., Grützmacher, Hansjörg, and Mindiola, Daniel J. A Scandium-Stabilized Diisophosphaethynolate Ligand: [OCPPCO] 4−. Germany: N. p., 2017. Web. doi:10.1002/ange.201710757.
Grant, Lauren N., Pinter, Balazs, Manor, Brian C., Grützmacher, Hansjörg, & Mindiola, Daniel J. A Scandium-Stabilized Diisophosphaethynolate Ligand: [OCPPCO] 4−. Germany. doi:10.1002/ange.201710757.
Grant, Lauren N., Pinter, Balazs, Manor, Brian C., Grützmacher, Hansjörg, and Mindiola, Daniel J. 2017. "A Scandium-Stabilized Diisophosphaethynolate Ligand: [OCPPCO] 4−". Germany. doi:10.1002/ange.201710757.
@article{osti_1414598,
title = {A Scandium-Stabilized Diisophosphaethynolate Ligand: [OCPPCO] 4−},
author = {Grant, Lauren N. and Pinter, Balazs and Manor, Brian C. and Grützmacher, Hansjörg and Mindiola, Daniel J.},
abstractNote = {},
doi = {10.1002/ange.201710757},
journal = {Angewandte Chemie},
number = 4,
volume = 130,
place = {Germany},
year = 2017,
month =
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on December 21, 2018
Publisher's Accepted Manuscript

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  • Scandium reacts with 4-(2-pyridylazo)resorcinol in the presence of monocarboxylic acids (X) to form mixed-ligand complexes with a Sc:PAR:x ratio of 1:2:2. The chemical nature of this interaction has been established, and the extraction of these mixed-ligand complexes has also been investigated; stability constants and molar extinction coefficients have been calculated. The values of the latter decrease in the order CH/sub 3/COOH > CH/sub 2/ClCOOH > CCl/sub 3/COOH. The formation and extraction of mixed-ligand complexes in Sc-PAR-HX systems make it possible to increase the sensitivity and selectivity of scandium determination in comparison with the use of the Sc-PAR mono-ligand complex.
  • Tris(acetylaceotnato)scandium(III) undergoes ligand exchange with the enolate form of acetylacetone in CD/sub 3/CN at 30-74/degree/C. The observed first-order rate constant, obtained by the /sup 1/H NMR method, is expressed by k/sub 0/ = k/sub 1//prime/(enol) + k/sub 2//prime/ at (complex) /approx equal/ 0.05 M. (Hacac) = 0.19 /minus/ 0.58 M, and (H/sub 2/O) = 0.026-0.26 M; k/sub 1//prime/ = 52 /plus minus/ 3 M/sup /minus/1/ s/sup /minus/1/ and k/sub 2//prime/ = 1.5 /plus minus/ 0.9 s/sup /minus/1/ at 56/degree/C. No water catalysis was observed. The k/sub 2//prime/ term is minor in the concentration region. The /Delta/H/double dagger/ and /Delta/S/double dagger/more » values for k/sub 1//prime/ are 36 /plus minus/ 5 kJ mol/sup /minus/1/ and /minus/105 /plus minus/ 16 J K/sup /minus/1/ mol/sup /minus/1/, respectively. The deuterium isotope effect k/sub 1//prime/(H)/k/sub 1//prime/(D) was significant (ca. 5). The I/sub a/ mechanism is assigned to the rate-determining formation of an intermediate containing a one-ended acac/sup /minus// and a unidentate Hacac in the enol form. 16 refs., 3 figs., 4 tabs.« less