title: Triorganophosphine-dithiomonometaphosphoryl halides.
abstract: The title compounds, ethyldiphenylphosphine-dithiomonometaphosphoryl chloride, EtPh(2)P-->PS(2)Cl, C(14)H(15)ClP(2)S(2), (I), and tris-n-propylphosphine-dithiomonometaphosphoryl chloride and bromide, nPr(3)P-->PS(2)Cl, C(9)H(21)ClP(2)S(2), (II), and nPr(3)P-->PS(2)Br, C(9)H(21)BrP(2)S(2), (III), respectively, are the first phosphine-stabilized dithiomonometaphosphoryl halides to be structurally characterized. In the tris-n-propylphosphine derivatives, the central P-->P donor-acceptor bond becomes longer in the order bromo < chloro < fluoro. Substitution of the tris-n-propylphosphine group in (II) by the more bulky ethyldiphenylphosphine group also leads to a longer P-->P bond. These structural features agree with the observed 31P NMR data. In (II) and (III), the central P-P bond coincides with the crystallographic threefold axis, entailing site-occupational disorder for the S(2)Y group.
authors.affiliation: Max Planck Institut für Chemische Physik fester Stoffe, Nöthnitzer Strasse 40, D-01187 Dresden, Germany.
authors.forename: Annegrit
authors.initials: A
authors.lastname: Rabis
authors.forename: Burkhard
authors.initials: B
authors.lastname: Ziemer
authors.forename: Dirk
authors.initials: D
authors.lastname: Wulff-Molder
authors.forename: Manfred
authors.initials: M
authors.lastname: Meisel
authors.forename: Sebastian
authors.initials: S
authors.lastname: Beck