Klaus Eichele Publication Abstracts 2013

 

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[UP]	C. Schädle, D. Schädle, K. Eichele, R. Anwander: Methylaluminium-stabilisierte Seltenerdmetalldihydride Angew. Chem. 2013, 125(50), 13480–13484. DOI 10.1002/ange.201306783

Der sterisch sehr anspruchsvolle Hydrotris(3-tert-butyl-5-methylpyrazolyl)borato-Ligand (Tp^tBu,Me) ermöglicht die Isolierung der Monolanthanoid-Komplexe [Tp^tBu,MeLn{(?-H)AlMe₃}₂] [Ln=Y, Lu (siehe Struktur)], die mit Dimethylanilin zu den diskreten, nicht agglomerierten Imid-Komplexen [Tp^tBu,MeLn{(?-NC₆H₃Me₂-2,6)(?-H)AlMe₂}] umgesetzt werden können. Die Ln-Hydrid-Bindung wird weiter mit ¹H-NMR-Spektroskopie über ¹H-⁸⁹Y-Kopplung und ⁸⁹Y-DEPT45-NMR-Experimente bestätigt.

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[UP]	C. Schädle, D. Schädle, K. Eichele, R. Anwander: Methylaluminum-Supported Rare-Earth-Metal Dihydrides Angew. Chem. Int. Ed. 2013, 52(50), 13238–13242. DOI 10.1002/anie.201306783

The super-bulky hydrotris(3-tert-butyl-5-methylpyrazolyl)borato ligand (Tp^tBu,Me) allows the isolation of the monolanthanide complexes [Tp^tBu,MeLn{(?-H)AlMe₃}₂] (Ln=Y, Lu; see structure), which can be transformed into discrete non-agglomerated imide complexes [Tp^tBu,MeLn{(?-NC₆H₃Me₂-2,6)(?-H)AlMe₂}] by reaction with dimethylaniline. Ln hydrido bonding is corroborated by ¹H NMR spectroscopy through ¹H–⁸⁹Y coupling and ⁸⁹Y DEPT45 NMR spectroscopy.

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[UP]	J. Arras, K. Eichele, L. Wesemann: Synthesis and Skeletal Transformations of Trinuclear Palladium and Nickel Phosphido Complexes Eur. J. Inorg. Chem. 2013(33), 5728–5737. DOI 10.1002/ejic.201300775

Trinuclear phosphido complexes of palladium and nickel were synthesized and characterized. [M{(2-Me₂NC₆H₄)PPh}(OAc)]₃ [M = Pd (2), Ni (6)] were obtained from the respective acetate, [Pd(OAc)₂]₃ or [Ni(OAc)₂(H₂O)₄], in reactions with the secondary aminophosphane (2-Me₂NC₆H₄)PHPh (1). The chloride derivative [Pd{(2-Me₂NC₆H₄)PPh}Cl]₃ (4a) was generated from the reaction of the chelating ligand 1 with Na₂PdCl₄. The reaction of the acetate 2 with p-toluenesulfonic acid (pTsOH) led to the formation of the tosylate analogue [Pd{(2-Me₂NC₆H₄)PPh}(OTs)]₃ (3). From the reaction of the tosylate trimer 3 with CsCl, CsBr or NaI, the substitution products [Pd{(2-Me₂NC₆H₄)PPh}X]₃ [X = Cl (4a), Br (4b), I (4c)] were isolated. From the reaction of the acetate 2 with HBF₄ or HClO₄ in acetonitrile, the solvent adduct [Pd(NP)(NCCH₃)]₃³⁺ was isolated as the BF₄^– (5a) or ClO₄^– salt (5b). The phosphido-bridged complexes were characterized by single-crystal structural analyses (2, 4, 5a and 6), solution NMR experiments, and in the case of 2 and 4a by solid-state ³¹P cross-polarization magic-angle spinning NMR spectroscopy. The crystal structures show the six-membered (MP)₃ cores in twist-boat or boat conformations that appear to be maintained in solution, according to NMR evidence. A search for (MP)₃ structures in the Cambridge Structural Database reveals that these two conformations are the most common ones (46 % twist-boat, 21 % boat, 17 % chair).