Coordination Complexes of Decamethylytterbocene with4,4'-Disubstituted Bipyridines: An Experimental Study of Spin Coupling inLanthanide Complexes

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The paramagnetic 1:1 coordination complexes of (C5Me5)2Ybwith a series of 4,4'-disubstituted bipyridines, bipy-X, where X is Me,tert-Bu, OMe, Ph, CO2Me, and CO2Et have been prepared. All of thecomplexes are paramagnetic and the values of the magnetic susceptibilityas a function of temperature show that these values are less thanexpected for the cation, [(C5Me5)2Yb(III)(bipy-X)]+, which have beenisolated as the cation-anion ion-pairs[(C5Me5)2Yb(III)(bipy-X)]+[(C5Me5)2YbI2]f fnfn where X is CO2Et, OMe andMe. The 1H NMR chemical shifts (293 K) for the methine resonances locatedat the 6,6' site in the bipy-X ring show a linear relationship with thevalues of chiT (300 K) for the neutral complexes which ... continued below

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Walter, Marc D.; Berg, David J. & Andersen, Richard A. December 8, 2005.

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The paramagnetic 1:1 coordination complexes of (C5Me5)2Ybwith a series of 4,4'-disubstituted bipyridines, bipy-X, where X is Me,tert-Bu, OMe, Ph, CO2Me, and CO2Et have been prepared. All of thecomplexes are paramagnetic and the values of the magnetic susceptibilityas a function of temperature show that these values are less thanexpected for the cation, [(C5Me5)2Yb(III)(bipy-X)]+, which have beenisolated as the cation-anion ion-pairs[(C5Me5)2Yb(III)(bipy-X)]+[(C5Me5)2YbI2]f fnfn where X is CO2Et, OMe andMe. The 1H NMR chemical shifts (293 K) for the methine resonances locatedat the 6,6' site in the bipy-X ring show a linear relationship with thevalues of chiT (300 K) for the neutral complexes which illustrates thatthe molecular behavior does not depend upon the phase with one exception,viz., (C5Me5)2Yb(bipy-Me). Single crystals of the 4,4'-dimethylbipyridinecomplex undergo an irreversible, abrupt first order phase change at 228 Kthat shatters the single crystals. The magnetic susceptibility,represented in a delta vs. T plot, on this complex, in polycrystallineform undergoes reversible abrupt changes in the temperature regime 205 -212 K, which is suggested to be due to the way the individual molec ularunits pack in the unit cell. A qualitative model is proposed thataccounts for the sub-normal magnetic moments in theseytterbocene-bipyridine complexes.

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  • Journal Name: Organometallics; Journal Volume: 25; Journal Issue: 13; Related Information: Journal Publication Date: June 19,2006

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  • Report No.: LBNL--61254
  • Grant Number: DE-AC02-05CH11231
  • Office of Scientific & Technical Information Report Number: 926705
  • Archival Resource Key: ark:/67531/metadc902009

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  • December 8, 2005

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  • Sept. 27, 2016, 1:39 a.m.

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  • Oct. 31, 2016, 3:49 p.m.

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Walter, Marc D.; Berg, David J. & Andersen, Richard A. Coordination Complexes of Decamethylytterbocene with4,4'-Disubstituted Bipyridines: An Experimental Study of Spin Coupling inLanthanide Complexes, article, December 8, 2005; Berkeley, California. (digital.library.unt.edu/ark:/67531/metadc902009/: accessed October 20, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.