Diolefins with an ether/thioether functionality as ligands in the coordination sphere of Ni and Rh.

Diolefins with an ether/thioether functionality as ligands in the coordination sphere of Ni and Rh.

Dalton transactions (Cambridge, England : 2003) (2015-11-04)

Crispin Lichtenberg, Jan Bloch, Thomas L Gianetti, Torsten Büttner, Jens Geier, Hansjörg Grützmacher

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.

MATERIALS

Product Number

Brand

Product Description

14664

Sigma-Aldrich

Triphenylphosphine, polymer-bound, 100-200 mesh, extent of labeling: ~3.2 mmol/g loading

93093

Sigma-Aldrich

Triphenylphosphine, polymer-bound, 100-200 mesh, extent of labeling: ~3 mmol/g triphenylphosphine loading

93094

Sigma-Aldrich

Triphenylphosphine, polymer-bound, 100-200 mesh, extent of labeling: ~1-1.5 mmol/g Capacity (Phosphor)

366455

Sigma-Aldrich

Triphenylphosphine, polymer-bound, 100-200 mesh, extent of labeling: ~3.0 mmol/g loading, 2 % cross-linked with divinylbenzene

T84409

Sigma-Aldrich

Triphenylphosphine, ReagentPlus^®, 99%

93092

Sigma-Aldrich

Triphenylphosphine, ≥95.0% (GC)