title: Study of the conformationally flexible, wide bite-angle diphosphine 4,6-bis(3-diisopropylphosphinophenyl)dibenzofuran in rhodium(I) and palladium(II) coordination complexes.
abstract: The diphosphine 4,6-bis(3-diisopropylphosphinophenyl)dibenzofuran (abbreviated as (iPr)DPDBFphos) was prepared and studied for its potential as a trans-chelating ligand in transition-metal coordination complexes. In the rhodium norbornadiene complex [((iPr)DPDBFphos)Rh(NBD)]BF(4), which has been characterized with multinuclear NMR spectroscopy, X-ray crystallography, and electrochemical studies, the ligand binds in cis fashion. In the bis(acetonitrile) complexes of rhodium and palladium [((iPr)DPDBFphos)M(CH(3)CN)(2)](BF(4))(n) (M = Rh, Pd; n = 1, 2), the ligand adopts a trans coordination geometry. Density functional theory (DFT, M06-L) calculations predict that the trans conformer is energetically more favorable than the cis by 3.5 kcal/mol. Cyclic voltammograms of the bis(acetonitrile) Pd(II) and Rh(I) complexes contain reversible and quasi-reversible reduction events, respectively, which are preliminarily assigned as metal-based redox reactions.
authors.affiliation: Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431, United States.
authors.forename: Keying
authors.initials: K
authors.lastname: Ding
authors.forename: Deanna L
authors.initials: DL
authors.lastname: Miller
authors.forename: Victor G
authors.initials: VG
authors.lastname: Young
authors.forename: Connie C
authors.initials: CC
authors.lastname: Lu
mesh_terms: D001572:Benzofurans / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*
chemical_list: D001572:Benzofurans; D009942:Organometallic Compounds; C558943:diphosphin 4,6-bis(3-diisopropylphosphinophenyl)dibenzofuran; D010165:Palladium; D012238:Rhodium