2026-06-15T03:08:50Zhttps://www.radar-service.eu/oai/OAIHandler10.35097/at7j6w642ryx7xq22026-06-10T14:42:49Zradar4kit
10.35097/at7j6w642ryx7xq2
Reitz, Cedric Y.
Cedric Y.
Reitz
0000-0001-8285-0815
Institut für Nukleare Entsorgung (INE), Karlsruher Institut für Technologie (KIT)
Frick, David
David
Frick
0000-0002-1345-1404
Institut für Anorganische Chemie (AOC), Karlsruher Institut für Technologie (KIT)
Pross, Elena
Elena
Pross
Institut für Anorganische Chemie (AOC), Karlsruher Institut für Technologie (KIT)
Reynolds, Emily M.
Emily M.
Reynolds
0000-0002-3546-2622
Institut für Nukleare Entsorgung (INE), Karlsruher Institut für Technologie (KIT)
Wansorra, Constantin
Constantin
Wansorra
0000-0002-7120-8322
Institut für Photonenforschung und Synchrotronstrahlung (IPS), Karlsruher Institut für Technologie (KIT)
Schenk, Sven M.
Sven M.
Schenk
0009-0007-1606-1472
Institut für Nukleare Entsorgung (INE), Karlsruher Institut für Technologie (KIT)
Branson, Jacob A.
Jacob A.
Branson
Institut für Nukleare Entsorgung (INE), Karlsruher Institut für Technologie (KIT)
Kaufmann-Heimeshoff, Hanna
Hanna
Kaufmann-Heimeshoff
Institut für Nukleare Entsorgung (INE), Karlsruher Institut für Technologie (KIT)
Blankenship, Mary
Mary
Blankenship
Institut für Photonenforschung und Synchrotronstrahlung (IPS), Karlsruher Institut für Technologie (KIT)
Wolf, Julius
Julius
Wolf
Institut für Anorganische Chemie (AOC), Karlsruher Institut für Technologie (KIT)
Hauschild, Dirk
Dirk
Hauschild
0000-0001-9088-8944
Institut für Photonenforschung und Synchrotronstrahlung (IPS), Karlsruher Institut für Technologie (KIT)
Göttlicher, Jörg
Jörg
Göttlicher
Institut für Photonenforschung und Synchrotronstrahlung (IPS), Karlsruher Institut für Technologie (KIT)
Steininger, Ralph
Ralph
Steininger
Institut für Photonenforschung und Synchrotronstrahlung (IPS), Karlsruher Institut für Technologie (KIT)
Mangold, Stefan
Stefan
Mangold
Institut für Photonenforschung und Synchrotronstrahlung (IPS), Karlsruher Institut für Technologie (KIT)
Ekanayake, Ruwini S. K.
Ruwini S. K.
Ekanayake
Institut für Nukleare Entsorgung (INE), Karlsruher Institut für Technologie (KIT)
Schacherl, Bianca
Bianca
Schacherl
0000-0003-4542-0108
Institut für Nukleare Entsorgung (INE), Karlsruher Institut für Technologie (KIT)
Heske, Clemens
Clemens
Heske
0000-0001-7586-4549
Institut für Photonenforschung und Synchrotronstrahlung (IPS), Karlsruher Institut für Technologie (KIT)
Celis-Barros, Cristian
Cristian
Celis-Barros
Ramanantoanina, Harry
Harry
Ramanantoanina
Institut für Nukleare Entsorgung (INE), Karlsruher Institut für Technologie (KIT)
Direct evidence of a lanthanide-tellurium bond in [K(18-crown 6)(Cp′′2LnTe3)] with Ln = La, Ce, and Nd
Karlsruhe Institute of Technology
2026
2026
Engineering
Open Access
Creative Commons Attribution Non Commercial No Derivatives 4.0 International
Reitz, Cedric Y.
0000-0001-8285-0815
Frick, David
0000-0002-1345-1404
Pross, Elena
Reynolds, Emily M.
0000-0002-3546-2622
Wansorra, Constantin
0000-0002-7120-8322
Schenk, Sven M.
0009-0007-1606-1472
Branson, Jacob A.
Kaufmann-Heimeshoff, Hanna
Blankenship, Mary
Wolf, Julius
Hauschild, Dirk
0000-0001-9088-8944
Göttlicher, Jörg
Steininger, Ralph
Mangold, Stefan
Ekanayake, Ruwini S. K.
Schacherl, Bianca
0000-0003-4542-0108
Heske, Clemens
0000-0001-7586-4549
Celis-Barros, Cristian
Ramanantoanina, Harry
Weinhardt, Lothar
0000-0003-3361-1054
Institut für Photonenforschung und Synchrotronstrahlung (IPS), Karlsruher Institut für Technologie (KIT)
Roesky, Peter W.
0000-0002-0915-3893
Institut für Anorganische Chemie (AOC), Karlsruher Institut für Technologie (KIT)
Vitova, Tonya
0000-0002-3117-7701
Institut für Nukleare Entsorgung (INE), Karlsruher Institut für Technologie (KIT)
Using non-classical divalent lanthanide precursors as multi-electron reducing agents, complexes, [K(18-crown-6)(Cp”2LnTe3)], with Ln = La, Ce, and Nd, Cp” = 1,3-bis-(trimethylsilyl)cyclopentadienyl, were synthesized and investigated to elucidate the mechanism of lanthanide-tellurium bonding and the role of 4f-element electron density in stabilizing small chalcogenide chains. Density-Functional Theory (DFT) reveals that the frontier molecular orbitals of these complexes are predominantly localized on the [Te3]2- fragment, while the trivalent lanthanide ions stabilize the tellurium chain through weak but measurable metal-ligand interactions. To experimentally resolve these interactions, we focus on complementary ligand- and metal-centered X-ray spectroscopic approaches. Ln L3-edge high-resolution XANES (HR-XANES) and valence-band resonant inelastic X-ray scattering (VB-RIXS) demonstrate that the Ln-Te/C interaction has substantial Ln 5d orbitals contribution, particularly for the Ln-Te bond, and remains largely constant across the three complexes. DFT-based bond analysis provides a mechanistic interpretation of these trends. The Ln–C interaction exhibits increasing electron density at the bond critical point and a higher delocalization index (QTAIM analysis) from the lighter to the heavier lanthanides, reflecting enhanced Ln 4f participation within an energy-driven covalency regime. The Ln–Te interaction is predominantly electrostatic, with meaningful orbital contributions arising mainly from Ln 5d participation within an orbital-overlap driven covalency regime. These results demonstrate that the Ln-C and Ln-Te bonding in the present complexes follow fundamentally distinct covalency mechanisms, which together enable the stabilization and isolation of the small [Te3]2- fragment chain.
Raw data from different spectroscopic methods used for the results in the publication and in the SI.
https://publikationen.bibliothek.kit.edu/1000192000
9,6 MB
application/x-tar