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Cooperative reduction by Ln2+ and Cp∗- ions : Synthesis and properties of Sm, Eu, and Yb complexes with 3,6-di-tert-butyl-o-benzoquinone. / Pushkarevsky, Nikolay A.; Ogienko, Mikhail A.; Smolentsev, Anton I. et al.
In: Dalton Transactions, Vol. 45, No. 3, 2016, p. 1269-1278.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Cooperative reduction by Ln2+ and Cp∗- ions
T2 - Synthesis and properties of Sm, Eu, and Yb complexes with 3,6-di-tert-butyl-o-benzoquinone
AU - Pushkarevsky, Nikolay A.
AU - Ogienko, Mikhail A.
AU - Smolentsev, Anton I.
AU - Novozhilov, Igor N.
AU - Witt, Alexander
AU - Khusniyarov, Marat M.
AU - Cherkasov, Vladimir K.
AU - Konchenko, Sergey N.
PY - 2016
Y1 - 2016
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84953911781&partnerID=8YFLogxK
U2 - 10.1039/c5dt03573b
DO - 10.1039/c5dt03573b
M3 - Article
AN - SCOPUS:84953911781
VL - 45
SP - 1269
EP - 1278
JO - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 3
ER -
ID: 25414518