Klaus Eichele Publication Abstracts 2018

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[UP]	J. Henoch, A. Auch, F. Diab, K. Eichele, H. Schubert, P. Sirsch, T. Block, R. Pöttgen, L. Wesemann: Cyclic Distannene or Bis(stannylene) with a Ferrocenyl Backbone: Synthesis, Structure, and Coordination Chemistry Inorg. Chem. 2018, 57(7), 4135-4145. DOI: 10.1021/acs.inorgchem.8b00317

1,1'-Dilithioferrocene was reacted with 2 equiv of isopropyl (Ar*) or methyl (Ar') substituted terphenyl tin(II) chloride. Reaction product 1, carrying the bulkier terphenyl substituent Ar*, displays a bis(stannylene) structure in the solid state without formation of a tin-tin bond. Temperature-dependent solution ¹¹⁹Sn NMR spectroscopy, however, revealed a dynamic interplay between bis(stannylene) (100 °C) and cyclic distannene (-80 °C). In contrast to 1, the less bulky Ar' substituent results in a cyclic distannene 2. On the basis of temperature-dependent ¹¹⁹Sn NMR spectroscopy the Sn-Sn bond of compound 2 was preserved up to 100 °C. Both compounds were further characterized by solid-state ¹¹⁹Sn NMR spectroscopy as well as ¹¹⁹Sn and ⁵⁷Fe Mössbauer spectroscopy. 1 reacted as a chelating ligand with nickel and palladium complexes [Ni(cod)₂] and [Pd(nbe)₃] (nbe = norbornene). In the resulting coordination compounds the nonstabilized stannylene acts as a donor as well as an acceptor ligand and shows a dynamic switch from donor to acceptor behavior in the monopalladium complex.

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[UP]	F. S. W. Aicher, K. Eichele, H. Schubert, L. Wesemann: Complete Hydrogen Transfer: Tin Hydride Reactivity toward Adamantylisonitrile and Benzonitrile Organometallics 2018, 37(11), 1773-1780. DOI: 10.1021/acs.organomet.8b00207

Adamantylisonitrile and benzonitrile were reacted with bulky substituted organotin trihydride [Ar*SnH3] [Ar* = (C6H3-2,6-Trip2), Trip = 2,4,6-triisopropylphenyl]. They do not show any reaction at room temperature as well as at 80 °C. After activation of the organotin trihydride with diethylmethylamine in the isonitrile case three hydrogen atoms were transferred from the tin atom to the isonitrile unit and a carbon tin bond was formed to give an intramolecular adduct between a diorganostannylene and a dialkylamine. Benzonitrile as well as adamantylisonitrile react both with low-valent organotin hydride [Ar*SnH]2. Benzonitrile shows an insertion reaction with the low-valent organotin hydride to yield a dimeric insertion product, whereas the isonitrile carbon atom of adamantylisonitrile abstracts three hydrogen atoms from the low-valent organotin hydride to give an equimolar mixture between (adamantylmethylamido)organostannylene and a bis(isonitrile)distannyne adduct.