title: Capture of phosphorus(I) and arsenic(I) moieties by a 1,2-bis(arylimino)acenaphthene (aryl-BIAN) ligand. A case of intramolecular charge transfer.
abstract: The reaction of PCl3 with SnCl2 in THF solution, followed by treatment with dpp-BIAN (dpp = 2,6-i-Pr2C6H3), affords the phosphenium complex [(dpp-BIAN)P][SnCl5.THF]. The 31P chemical shift (delta 232.5) and the metrical parameters from a single-crystal X-ray diffraction study indicate that the oxidation state of phosphorus in this compound is +3. A similar conclusion was reached regarding the phosphorus oxidation state in [(dpp-BIAN)P][I3], which was prepared via the reaction of dpp-BIAN with PI3 in CH2Cl2 solution. The arsenium salt [(dpp-BIAN)As][SnCl5.THF] was prepared by treatment of AsCl3 with SnCl2 in THF solution, followed by the addition of dpp-BIAN. The X-ray crystal structure of this salt was determined, and the pattern of bond distances and angles indicates that arsenic is present in the +3 oxidation state.
authors.affiliation: Department of Chemistry and Biochemistry, The University of Texas at Austin, 1 University Station A5300, Austin, TX 78712-0165, USA.
authors.forename: Gregor
authors.initials: G
authors.lastname: Reeske
authors.forename: Clint R
authors.initials: CR
authors.lastname: Hoberg
authors.forename: Nicholas J
authors.initials: NJ
authors.lastname: Hill
authors.forename: Alan H
authors.initials: AH
authors.lastname: Cowley