Triorganophosphine-dithiomonometaphosphoryl halides.
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.
Rabis
Annegrit
A
Max Planck Institut für Chemische Physik fester Stoffe, Nöthnitzer Strasse 40, D-01187 Dresden, Germany.
Ziemer
Burkhard
B
Wulff-Molder
Dirk
D
Meisel
Manfred
M
Beck
Sebastian
S