Hybrid alpha-Diimine/Bis(chalcogenoether) Ligands for Copper(I) an Copper(II) Complexes
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F18%3A00492505" target="_blank" >RIV/61388955:_____/18:00492505 - isvavai.cz</a>
Result on the web
<a href="http://dx.doi.org/10.1002/zaac.201800073" target="_blank" >http://dx.doi.org/10.1002/zaac.201800073</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/zaac.201800073" target="_blank" >10.1002/zaac.201800073</a>
Alternative languages
Result language
angličtina
Original language name
Hybrid alpha-Diimine/Bis(chalcogenoether) Ligands for Copper(I) an Copper(II) Complexes
Original language description
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.
Czech name
—
Czech description
—
Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2018
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Zeitschrift für anorganische und allgemeine Chemie
ISSN
0044-2313
e-ISSN
—
Volume of the periodical
644
Issue of the periodical within the volume
14
Country of publishing house
DE - GERMANY
Number of pages
10
Pages from-to
661-670
UT code for WoS article
000440311100009
EID of the result in the Scopus database
2-s2.0-85050799311