title: Diolefins with an ether/thioether functionality as ligands in the coordination sphere of Ni and Rh.
abstract: A diolefin ether, trop2O (2), and a diolefin thioether, trop2S (3), have been investigated as ligand analogues of the well-established diolefin amine, trop2NH (1). Compounds 2 and 3 form different conformers in solution and in the solid state. Whereas 2 could be coordinated to Ni(0), 3 was found to be more suited for coordination to Rh(I). The coordination chemistry, electrochemical properties, and ligand exchange phenomena of the resulting complexes, [Ni(trop2O)(PPh3)] (5) and [Rh(trop2S)(L)n][OTf] (6: L = NCMe, n = 2; 7: L = 2,2'-bipy, n = 1) were investigated by analytical techniques including NMR spectroscopy, single crystal X-ray analysis, and cyclic voltammetry. The results were compared with those obtained for the amine analogues of 5, 6, and 7.
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich, Switzerland. hgruetzmacher@ethz.ch.
authors.forename: Crispin
authors.initials: C
authors.lastname: Lichtenberg
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich, Switzerland. hgruetzmacher@ethz.ch.
authors.forename: Jan
authors.initials: J
authors.lastname: Bloch
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich, Switzerland. hgruetzmacher@ethz.ch.
authors.forename: Thomas L
authors.initials: TL
authors.lastname: Gianetti
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich, Switzerland. hgruetzmacher@ethz.ch.
authors.forename: Torsten
authors.initials: T
authors.lastname: Büttner
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich, Switzerland. hgruetzmacher@ethz.ch.
authors.forename: Jens
authors.initials: J
authors.lastname: Geier
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich, Switzerland. hgruetzmacher@ethz.ch.
authors.forename: Hansjörg
authors.initials: H
authors.lastname: Grützmacher