title: Model complexes for metallated polythiophenes: gold(I) and palladium(II) complexes of bis(diphenylphosphino)oligothiophenes.
abstract: The preparations of two new phosphinothiophene ligands, 3,3'-bis(diphenylphosphino)-2,2'-bithiophene (dppbt; 1) and 3,3' "-dihexyl-3',3' '-bis(diphenylphosphino)-2,5':2',2' ':5' ',2' "-quaterthiophene (hdppqt; 2) are reported. Oxidation of 1 gives 3,3'-bis(diphenylphosphine oxide)-2,2'-bithiophene (3), and the crystal structure of this compound was determined. Pd(II) and Au(I) complexes of these ligands have been synthesized and characterized. Crystal structures of [(dppbt)PdCl(2)] (1-Pd), [(hdppqt)PdCl(2)] (2-Pd), [(dppbt)(AuCl)(2)] (1-Au), and [(hdppqt)(AuCl)(2)] (2-Au) were obtained. [(dppbt)(AuCl)(2)] crystallized in two solid-state forms; crystals grown from CH(2)Cl(2)/Et(2)O show a gold-gold interaction of 3.3221(4) A, but from CH(2)Cl(2)/toluene, the molecule crystallizes as a toluene adduct (1-Au-tol) and does not show any gold-gold interaction. All the complexes were characterized via UV-vis spectroscopy and cyclic voltammetry, and the effect of the metal on the energy of the pi-pi transition and oxidation potential was determined. These data are correlated to the interannular torsion angles in the oligothienyl groups from the crystal structure studies.
authors.affiliation: Department of Chemistry, The University of British Columbia, Vancouver, British Columbia, Canada V6T 1Z1.
authors.forename: Olivier
authors.initials: O
authors.lastname: Clot
authors.forename: Yumi
authors.initials: Y
authors.lastname: Akahori
authors.forename: Carolyn
authors.initials: C
authors.lastname: Moorlag
authors.forename: Daniel B
authors.initials: DB
authors.lastname: Leznoff
authors.forename: Michael O
authors.initials: MO
authors.lastname: Wolf
authors.forename: Raymond J
authors.initials: RJ
authors.lastname: Batchelor
authors.forename: Brian O
authors.initials: BO
authors.lastname: Patrick
authors.forename: Mikita
authors.initials: M
authors.lastname: Ishii