Diolefins with an ether/thioether functionality as ligands in the coordination sphere of Ni and Rh. Issue 46 (3rd November 2015)

• Record Type: Journal Article
• Authors: Lichtenberg, Crispin; Bloch, Jan; Gianetti, Thomas L.; Büttner, Torsten; Geier, Jens; Grützmacher, Hansjörg
• Is Part Of: Dalton transactions. Volume 44:Issue 46(2015)
• Page Start: 20056
• Page End: 20066
• Publication Date: 2015-11-03
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c5dt03279b
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : A diolefin ether, trop2 O, and a diolefin thioether, trop2 S, were prepared and coordinated to Ni(0) or Rh(i ). A comparison of the electrochemical data with corresponding amine diolefin complexes reveal the differences in stabilizing various oxidation states of these complexes. Abstract : A diolefin ether, trop2 O (2 ), and a diolefin thioether, trop2 S (3 ), have been investigated as ligand analogues of the well-established diolefin amine, trop2 NH (1 ). Compounds2 and3 form different conformers in solution and in the solid state. Whereas2 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(trop2 O)(PPh3 )] (5 ) and [Rh(trop2 S)(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 of5, 6, and7 .