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Hybrid alpha-Diimine/Bis(chalcogenoether) Ligands for Copper(I) an Copper(II) Complexes
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SYSNO ASEP 0492505 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Hybrid alpha-Diimine/Bis(chalcogenoether) Ligands for Copper(I) an Copper(II) Complexes Tvůrce(i) Bubrin, M. (DE)
Kvapilová, Hana (UFCH-W) RID
Fiedler, Jan (UFCH-W) RID, ORCID
Ehret, F. (DE)
Záliš, Stanislav (UFCH-W) RID, ORCID
Kaim, W. (DE)Zdroj.dok. Zeitschrift für anorganische und allgemeine Chemie. - : Wiley - ISSN 0044-2313
Roč. 644, č. 14 (2018), s. 661-670Poč.str. 10 s. Jazyk dok. eng - angličtina Země vyd. DE - Německo Klíč. slova cambridge structural database ; crystal-structures ; coordination chemistry ; systems ; epr ; proteins ; spectroelectrochemistry ; oxidation ; energies ; alcohols Vědní obor RIV CF - Fyzikální chemie a teoretická chemie Obor OECD Physical chemistry CEP LTC17052 GA MŠMT - Ministerstvo školství, mládeže a tělovýchovy GA18-09848S GA ČR - Grantová agentura ČR Způsob publikování Omezený přístup Institucionální podpora UFCH-W - RVO:61388955 UT WOS 000440311100009 EID SCOPUS 85050799311 DOI 10.1002/zaac.201800073 Anotace The new ligands L = 1,4-bis(2-methylchalcogenophenyl)-2,3-dimethyl-1,4-diaza-1,3-diene [chalcogen = O (1), S (2) or Se (3)] have been studied in their coordination behavior towards Cu-I and Cu-II. Whereas the O-ether containing ligand forms complex ions [Cu(L)(2)](n+) = 4(n+), with exclusive N-coordination (n = 1) or N and weaker O coordination (n = 2), the species with E = S or Se contain tetradentate ligands in [Cu(L)](+) (5(+), 6(+)) and [Cu(L)L'](n+) [n = 1, L' = TfO- (E = S) or n = 2 and L' = H2O (E = Se)]. Molecular structures in the crystals of 5(+) and 6(+) show distorted tetrahedral N coordination at the metal and innocently behaving alpha-diimine functions, in agreement with spectroscopic and computational data. The copper(II) ions [Cu(L)L'](2+) with one tetradentate ligand L = 2 or 3 exhibit a square-pyramidal configuration at the metal. Two isolated crystalline forms of 4(2+) show weak coordination (2.636-2.96 angstrom) of three or four ether oxygen atoms, resulting in 4+3 or 4+4 coordination arrangements for N and O donors, respectively. In agreement with the rather different Cu-I and Cu-II structures the electrochemical oxidation of the copper(I) complexes and the reduction of the corresponding Cu-II species reveal an ECEC behavior within a square scheme, whereas the reduction of the Cu-I compounds, most likely at the diimine site, proceeds irreversibly. UV/Vis spectroelectrochemical results showing intense MLCT and IL absorptions were analyzed with the help of TD-DFT calculations. Pracoviště Ústav fyzikální chemie J.Heyrovského Kontakt Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Rok sběru 2019 Elektronická adresa http://hdl.handle.net/11104/0286012
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