Chemistry of the f-elements
PD Dr. habil. Moritz Schmidt
Head Chemistry of the f-elements
+49 351 260 3156, +49 351 260 2536
Bautzner Landstraße 400 - 01328 Dresden
Current:Head of the department "Chemistry of the f-elements" Helmholtz-Zentrum Dresden-Rossendorf (HZDR), Institute of Resource Ecology.
2013 – 2018:Helmholtz Young Investigator group leader at the Helmholtz-Zentrum Dresden-Rossendorf (HZDR), Institute of Resource Ecology.
2012 – 2013:Research associate at the Karlsruhe Institute of Technology (KIT), Institute for Nuclear Waste Disposal.
2010 – 2012:Research Associate at Argonne National Laboratory (ANL), Chemical Sciences and Engineering Division.
11/2009:PhD at the University of Heidelberg, Department of Chemistry, “Untersuchungen zum Einbaumechanismus von Actiniden und Lanthaniden in Calcium-haltige Sekundärphasen” (in German).
2006 – 2009:PhD student at the Forschungszentrum Karlsruhe, Institute for Nuclear Waste Disposal.
2006:Diplom (M.Sc.) in Chemistry at the University of Heidelberg
- Actinide chemistry
- Geochemistry of the actinides in the context of nuclear waste storage
- Mineral/water interface reactions
- Structural incorporation of actinides into mineral phases
- Site-selective time-resolved laser fluorescence spectroscopy with Cm(III) and Eu(III)
- Surface X-ray diffraction
Newest Publication in the Department
Pd–Si complexes of the type ClPd(μ²-pyO)₄SiR (R = Me, Ph, Bn, Allyl, κO-(pyO)PdCl(η³-allyl); pyO = pyridine-2-olate): The influence of substituent R on the Pd–Si bond
The reactions of organosiliconpyridine-2-olates (pyridyl-2-oxysilanes) RSi(pyO)₃ (pyO = pyridine-2-olate, R = Me (1a), Ph (1b), Bn (1c) and Allyl (1d)) and [PdCl₂(NCMe)₂] in chloroform afforded the hexacoordinate silicon complexes RSi(μ²-pyO)₄PdCl (R = Me (2a), Ph (2b), Bn (2c) and Allyl (2d), respectively), which feature a Pd–Si bond, in which the Pd atom is the formal lone pair donor toward Si. The new compounds 2b, 2c, 2d were characterized with multi-nuclear NMR spectroscopy and elemental analysis. The effect of the Si-bound substituent R on the trans-disposed Pd–Si bond was studied by single-crystal X-ray diffraction and computational analyses (e.g., Natural Localized Molecular Orbitals, NLMO; topological analyses of the electron density at the bond critical point with Quantum Theory of Atoms-In-Molecules, QTAIM). A structurally related byproduct, (η³-allyl) ClPd(pyO)Si(μ²-pyO)₄PdCl 2d’, which formed along with target product 2d and features an Si–O bond trans to Pd–Si, was included in this systematic study. Another byproduct from the synthesis of 2d, the pentanuclear complex ClPd(μ²-pyO)₂Si(μ²-pyO)₂Pd(μ²-pyO)₂Si(μ²-pyO)₂PdCl (compound 3) was characterized crystallographically. This compound features pentacoordinate Si atoms within trigonal–bipyramidal Si(O₄Pd) coordination spheres with equatorial Pd–Si bonds to the terminal Pd atoms. The Pd–Si bond situation in this compound was elucidated with the aid of computational analyses. QTAIM analyses of 3 in conjunction with a model compound PdSi4, which features two silyl groups and two silylene ligands, indicate topological properties of the electron density at the Pd–Si bond critical point which are similar to Pd–Si bonds of silyl and silylene compounds. The latter exhibit greater similarity, which indicates features of a Pd←Si bond. In contrast, NLMO analyses of 3 identify a polar covalent Pd–Si bond with predominant Pd contribution (formal Pd→Si donation).
Keywords: Ambidentate ligands; Hypercoordination; NMR spectroscopy; Palladium; Silicon; Single-crystal X-ray diffraction; Topological analysis
Polyhedron 245(2023), 116663
Online First (2023) DOI: 10.1016/j.poly.2023.116663
- f-Char (02NUK059B), German Federal Ministry of Education and Research, 2019 - 2023.
- SMILE (02E11668B), German Federal Ministry of the Economy, 2018 - 2022.
- FENABIUM (02NUK046B), German Federal Ministry of Education and Research, 2016-2021.
- Helmholtz Young Investigator Group “Structures and reactivity at the aqueous/mineral interface”, (VH-NG-942), Helmholtz Association, 2013 - 2018.