Callaghan Innovation Research Papers

Back to Research Papers

TitleDerivatized cyclophane chemistry. Synthesis of new (π-benzene)ruthenium(II) complexes of 2,11-dithia- and 2,11-diselena[3.3]orthocyclophane
Publication TypeJournal Article
Year of Publication1993
AuthorsHanton, L.R., and Kemmitt T.
JournalInorganic Chemistry
Pagination3648 - 3653
Date Published1993
ISSN00201669 (ISSN)
AbstractThe reactions of [(η6-C6H6)Ru(acetone)3][BF 4]2 with 2,11-dithia- (1) and 2,11-diselena[3.3]orthocyclophane (2) were used to prepare the complexes [(η6-C6H6)Ru(E-E)(L)] [BF4]2 and [(η6-C6H6)Ru(E-E)(X)]X (E-E = 1, 2; L = MeCN, EtCN; X = Cl, Br). The complexes were characterized by microanalysis and 1H and 13C NMR and IR spectroscopy. The molecular structure of [(η6-C6H6)Ru(1)(EtCN)] [BF4]2 (3) was determined. Crystals of 3 belong to the space group P21/n with a = 11.670(3) Å, b = 19.893(5) Å, c = 12.038(5) Å, β = 104.71(3)°, V = 2703(2) Å3, and Z = 4. The structure was refined to Rw = 3.63% and Rw = 3.91% for 4437 with I > 2.5σ(I). The Ru atom is six-coordinate. 1 acts as a chelating ligand via the S donor atoms and adopts a rigid anti-II conformation. The Ru-N-C angle is 166.0(3)°, and the bending may reflect π-donation by EtCN or crystal packing forces. The solid-state structure consists of sheets of π-interacting cations. Each arene ring of 3 is involved in a π-π interaction with an arene ring on an adjacent cation. The complexes containing MeCN are labile in solution, but those containing EtCN are not. Both nitriles can be displaced by halides. The MeCN complexes can extract low concentrations of EtCN from nitromethane. The complexes of 2 are the first examples of (selenoether)(π-benzene)ruthenium(II) compounds. © 1993 American Chemical Society.

Back to top