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Title: Influence of the Torsion Angle in 3,3'-Dimethyl-2,2'-bipyridine on the Intermediate Valence of Yb in (C5Me5)2 Yb(3,3'-Me2-bipy)

Abstract

The synthesis and X-ray crystal structures of Cp-2*Yb(3,3'-Me(2)bipy) and [Cp-2 Yb(3,3'-Me(2)bipy)][Cp-2 YbCl1.6I0.4]center dot CH2Cl2 are described. In both complexes, the NCCN torsion angles are approximately 40 degrees. The temperature-independent value of n(f) of 0.17 shows that the valence of ytterbium in the neutral adduct is multiconfigurational, in reasonable agreement with a CASSCF calculation that yields a n(f) value of 0.27; that is, the two configurations in the wave function are f(13)(pi(1))(1) and f(14)(pi(1))(0) in a ratio of 0.27:0.73, respectively, and the open-shell singlet lies 0.28 eV below the triplet state (n(f) accounts for f-hole occupancy; that is, n(f) = 1 when the configuration is f(13) and n(f) = 0 when the configuration is f(14)). A correlation is outlined between the value of nf and the individual ytterbocene and bipyridine fragments such that, as the reduction potentials of the ytterbocene cation and the free x,x'-R-2-bipy ligands approach each other, the value of nf and therefore the f(13):f(14) ratio reaches a maximum; conversely, the ratio is minimized as the disparity increases.

Authors:
; ; ;
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
Chemical Sciences Division
OSTI Identifier:
1163867
Report Number(s):
LBNL-6698E
DOE Contract Number:  
DE-AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 32; Journal Issue: 19; Related Information: Journal Publication Date: 2013
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; DECAMETHYLYTTERBOCENE COMPLEXES; DIPERCHLORATE MONOHYDRATE; LANTHANIDE COMPLEXES; GROUND-STATE; BIPYRIDINES; 1,1'-BIISOQUINOLINE; COORDINATION; COVALENCY; EXCHANGE

Citation Formats

Nocton, Gré, gory,, Booth, Corwin H., Maron, Laurent, and Andersen, Richard A. Influence of the Torsion Angle in 3,3'-Dimethyl-2,2'-bipyridine on the Intermediate Valence of Yb in (C5Me5)2 Yb(3,3'-Me2-bipy). United States: N. p., 2014. Web.
Nocton, Gré, gory,, Booth, Corwin H., Maron, Laurent, & Andersen, Richard A. Influence of the Torsion Angle in 3,3'-Dimethyl-2,2'-bipyridine on the Intermediate Valence of Yb in (C5Me5)2 Yb(3,3'-Me2-bipy). United States.
Nocton, Gré, gory,, Booth, Corwin H., Maron, Laurent, and Andersen, Richard A. Thu . "Influence of the Torsion Angle in 3,3'-Dimethyl-2,2'-bipyridine on the Intermediate Valence of Yb in (C5Me5)2 Yb(3,3'-Me2-bipy)". United States. https://www.osti.gov/servlets/purl/1163867.
@article{osti_1163867,
title = {Influence of the Torsion Angle in 3,3'-Dimethyl-2,2'-bipyridine on the Intermediate Valence of Yb in (C5Me5)2 Yb(3,3'-Me2-bipy)},
author = {Nocton, Gré and gory, and Booth, Corwin H. and Maron, Laurent and Andersen, Richard A.},
abstractNote = {The synthesis and X-ray crystal structures of Cp-2*Yb(3,3'-Me(2)bipy) and [Cp-2 Yb(3,3'-Me(2)bipy)][Cp-2 YbCl1.6I0.4]center dot CH2Cl2 are described. In both complexes, the NCCN torsion angles are approximately 40 degrees. The temperature-independent value of n(f) of 0.17 shows that the valence of ytterbium in the neutral adduct is multiconfigurational, in reasonable agreement with a CASSCF calculation that yields a n(f) value of 0.27; that is, the two configurations in the wave function are f(13)(pi(1))(1) and f(14)(pi(1))(0) in a ratio of 0.27:0.73, respectively, and the open-shell singlet lies 0.28 eV below the triplet state (n(f) accounts for f-hole occupancy; that is, n(f) = 1 when the configuration is f(13) and n(f) = 0 when the configuration is f(14)). A correlation is outlined between the value of nf and the individual ytterbocene and bipyridine fragments such that, as the reduction potentials of the ytterbocene cation and the free x,x'-R-2-bipy ligands approach each other, the value of nf and therefore the f(13):f(14) ratio reaches a maximum; conversely, the ratio is minimized as the disparity increases.},
doi = {},
journal = {Organometallics},
number = 19,
volume = 32,
place = {United States},
year = {2014},
month = {6}
}