Reduction chemistry of En ligand complexes with maingroup and f-element compounds
Final Report Abstract
In a fundamental project, the interaction of polypnictogenides coordinated to transition metals with compounds of the alkali metals and the lanthanides was investigated. In the first funding period, we essentially succeeded in establishing d-f metal complexes with polyphosphides. For this purpose, treatment of En-ligand complexes with low-valent rare-earth element complexes was implemented as basic synthesis strategy. This usually results in the reduction of the En-ligand complex and the formation of the desired mixed d-f metal compound. In this context, we discovered a surprisingly similar reactivity of the En-ligand complexes with alkali metals and comparable reactive compounds. In the second funding period, our work with the element phosphorus as a pnictogenide was continued. However, the main focus laid essentially on with En-ligand complexes of the heavy pnictogenides (mainly As, but also Sb). The emphasis of the proposal was, on the one hand, the synthesis of new pnictogenide f-metal complexes starting from En-ligand complexes. On the other hand, the reduction behavior of En-ligand complexes towards s-block element compounds and the reaction behavior of the resulting products were studied. Although the reactivity of En-ligand complexes toward d-block compounds has been well studied, their reactivity towards f-elements and alkali metal compounds had also not received attention prior to our work.
Publications
- Open Chain Polyarsenides of the Lanthanides Chem. Eur. J. 2018, 24, 7890-7895
C. Schoo, R. Köppe, M. Piesch, M. T. Gamer, S. N. Konchenko, M. Scheer, P. W. Roesky
(See online at https://doi.org/10.1002/chem.201800539) - Element-Element Bond Formation upon Oxidation and Reduction Angew. Chem. 2020, 132, 7220-7227. Angew. Chem. Int. Ed. 2020, 59, 7154-7160
M. Piesch, Ch. Graßl, M. Scheer
(See online at https://doi.org/10.1002/ange.201916622 https://doi.org/10.1002/anie.201916622) - Highly Selective Substitution and Insertion Reactions of Silylenes in a Metal-Coordinated Polyphosphide J. Am. Chem. Soc. 2020, 142, 1190-1195
R. Yadav, T. Simler, S. Reichl, B. Goswami, C. Schoo, R. Köppe, M. Scheer P. W. Roesky
(See online at https://doi.org/10.1021/jacs.9b12151) - Regioselective Insertion of Aluminium(I) in the cyclo-P5 Ring of Pentaphosphaferrocene Angew. Chem. 2020, 132, 9530-9534. Angew. Chem. Int. Ed. 2020, 59, 9443-9447
R. Yadav, T. Simler, B. Goswami, C. Schoo, R. Köppe, S. Dey, P. W. Roesky
(See online at https://doi.org/10.1002/ange.202002774 https://doi.org/10.1002/anie.202002774) - Transformations of the cyclo-P4 Ligand in [Cp’’’Co(η4-P4)] Chem. Sci. 2020, 11, 6745-6751
M. Piesch, M. Seidl, M. Scheer
(See online at https://doi.org/10.1039/d0sc01740j) - A Structural Diversity of Molecular Alkaline-Earth-Metal Polyphosphides: From Supramolecular Wheel to Zintl Ion Chem. Eur. J. 2021, 27, 14128-14137
R. Yadav, M. Weber, A. K. Singh, L. Münzfeld, J. Gramüller, R. M. Gschwind, M. Scheer, P. W. Roesky
(See online at https://doi.org/10.1002/chem.202102355) - d/f-Polypnictides Derived by Non-Classical Ln2+ Compounds: Synthesis, Small Molecule Activation and Optical Properties Chem. Eur. J. 2021, 27, 7862–7871
N. Reinfandt, N. Michenfelder C. Schoo, R. Yadav, S. Reichl, S. N. Konchenko, A. N. Unterreiner, M. Scheer, P. W. Roesky
(See online at https://doi.org/10.1002/chem.202100605) - Redox Chemistry of Heterobimetallic Polypnictogen Triple-Decker Complexes – Rearrangement, Fragmentation and Transfer Chem. Eur. J. 2021, 27, 9129-9140
M. Piesch, S. Reichl, Ch. Riesinger, M. Seidl, G. Balazs, M. Scheer
(See online at https://doi.org/10.1002/chem.202100844) - Synthesis and Reactivity of Anionic cyclo-E3 (E = P, As) Ligand Complexes Angew. Chem. 2021, 133, 15228-15236. Angew. Chem. Int. Ed. 2021, 60, 15101-15108
M. Piesch, S. Reichl, M. Seidl, G. Balazs, M. Scheer
(See online at https://doi.org/10.1002/angew.202103683 https://doi.org/10.1002/anie.202103683) - Synthesis of unprecedented 4d/4f-polypnictogens Chem. Eur. J. 2021, 27, 3974-3978
N. Reinfandt, C. Schoo, L. Dütsch, R. Köppe, S. N. Konchenko, M. Scheer, P. W. Roesky
(See online at https://doi.org/10.1002/chem.202003905)
