Cooperative Reduction by Ln2+ and Cp*− ions: Synthesis and Properties of Sm, Eu, and Yb Complexes with 3,6-di-tert-butyl-o-benzoquinone Full article
Journal |
Dalton Transactions
ISSN: 1477-9226 , E-ISSN: 1477-9234 |
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Output data | Year: 2016, Volume: 45, Number: 3, Pages: 1269-1278 Pages count : 10 DOI: 10.1039/c5dt03573b | ||||||||||
Tags | METAL-CATECHOL COMPLEXES; SINGLE-MOLECULE MAGNETS; LANTHANIDE COMPLEXES; REDOX CHEMISTRY; APROTIC MEDIA; ELECTROCHEMICAL REDUCTION; SEMIQUINONE COMPLEXES; INTERMEDIATE-VALENCE; UNIQUE PROPERTIES; STRONG EXCHANGE | ||||||||||
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Abstract:
The first examples of samarium, europium, and ytterbium complexes with 3,6-di-tert-butyl-o-benzoquinone (3,6-dbbq) in the form of catecholate have been obtained by reactions of the quinone with the corresponding lanthanocenes, (n = 1 or 2) in solution. In the course of the reactions lanthanide ions lose one or two Cp∗ ligands, which take part in reduction of a quinone molecule into a catecholate anion (dbcat, 2-). As a result of the reactions, Sm and Yb clearly yield dimeric complexes [(LnCp∗)2(dbcat)2], where each Ln ion loses one Cp∗ ligand. Eu forms a trimeric complex [(EuCp∗)(Eu·thf)2(dbcat)3], in which one Eu ion is coordinated by one Cp∗ ligand, while two Eu ions have lost all Cp∗ ligands and are coordinated by THF molecules instead. Magnetic properties corroborate the assignment of oxidation states made on the basis of single-crystal X-ray diffraction: all the quinone ligands are present in the catecholate state; both Sm/Yb ions in the dimers are in the +3 oxidation state, whereas the Eu trimer contains two Eu(ii) and one Eu(iii) ions. Cyclovoltammetry studies show the presence of two reversible oxidation waves for all complexes, presumably concerned with the redox transitions of the dbcat ligands. © 2016 The Royal Society of Chemistry.
Cite:
Pushkarevsky N.A.
, Ogienko M.A.
, Smolentsev A.I.
, Novozhilov I.N.
, Witt A.
, Khusniyarov M.M.
, Cherkasov V.K.
, Konchenko S.N.
Cooperative Reduction by Ln2+ and Cp*− ions: Synthesis and Properties of Sm, Eu, and Yb Complexes with 3,6-di-tert-butyl-o-benzoquinone
Dalton Transactions. 2016. V.45. N3. P.1269-1278. DOI: 10.1039/c5dt03573b WOS Scopus РИНЦ
Cooperative Reduction by Ln2+ and Cp*− ions: Synthesis and Properties of Sm, Eu, and Yb Complexes with 3,6-di-tert-butyl-o-benzoquinone
Dalton Transactions. 2016. V.45. N3. P.1269-1278. DOI: 10.1039/c5dt03573b WOS Scopus РИНЦ
Files:
Full text from publisher
Dates:
Submitted: | Sep 12, 2015 |
Accepted: | Nov 29, 2015 |
Published online: | Dec 1, 2015 |
Identifiers:
Web of science | WOS:000367614700049 |
Scopus | 2-s2.0-84953911781 |
Elibrary | 26945819 |
Chemical Abstracts | 2015:1926722 |
Chemical Abstracts (print) | 164:127141 |
OpenAlex | W2185252236 |