Intermediate-Valence Tautomerism in Decamethylytterbocene Complexes of Methyl-Substituted Bipyridines

被引：89

作者：

Booth, Corwin H. ^{[1
]}

Kazhdan, Daniel ^{[1
,2
]}

Werkema, Evan L. ^{[1
,2
]}

Walter, Marc D. ^{[1
,2
]}

Lukens, Wayne W. ^{[1
]}

Bauer, Eric D. ^{[3
]}

Hu, Yung-Jin ^{[2
,4
]}

Maron, Laurent ^{[5
,6
]}

Eisenstein, Odile ^{[6
]}

Head-Gordon, Martin ^{[1
,2
]}

Andersen, Richard A. ^{[1
,2
]}

机构：

[1] Univ Calif Berkeley, Lawrence Berkeley Lab, Div Chem Sci, Berkeley, CA 94720 USA

[2] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA

[3] Los Alamos Natl Lab, Mat Phys & Applicat Div, Los Alamos, NM 87545 USA

[4] Univ Calif Berkeley, Lawrence Berkeley Lab, Div Nucl Sci, Berkeley, CA 94720 USA

[5] Univ Toulouse, INSA UPS LPCNO, F-31077 Toulouse, France

[6] Univ Montpellier 2, Inst Charles Gerhardt, CNRS UMR 5253, F-34095 Montpellier, France

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2010年 / 132卷 / 49期

关键词：

COUPLED CASPT2 CALCULATIONS; AB-INITIO PSEUDOPOTENTIALS; LANTHANIDE COMPLEXES; ELECTRONIC-STRUCTURE; OXIDATION-STATE; GROUND-STATES; ION STATES; SPIN; CEROCENE; COORDINATION;

D O I：

10.1021/ja106902s

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Multiconfigurational, intermediate valent ground states are established in several methyl-substituted bipyridine complexes of bis(pentamethylcyclopentadienyl)ytterbium, Cp-2*Yb (Me-x-bipy). In contrast to Cp-2*Yb(bipy) and other substituted-bipy complexes, the nature of both the ground state and the first excited state are altered by changing the position of the methyl or dimethyl substitutions on the bipyridine rings. In particular, certain substitutions result in multiconfigurational, intermediate valent open-shell singlet states in both the ground state and the first excited state. These conclusions are reached after consideration of single-crystal X-ray diffraction (XRD), the temperature dependence of X-ray absorption near-edge structure (XANES), extended X-ray absorption fine-structure (EXAFS), and magnetic susceptibility data, and are supported by CASSCF-MP2 calculations. These results place the various Cp-2*Yb(bipy) complexes in a new tautomeric class, that is, intermediate-valence tautomers.

引用

页码：17537 / 17549

页数：13

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