METAL-PURINE INTERACTIONS - HOMODINUCLEAR AND HETERODINUCLEAR PLATINUM(II) AND OR PALLADIUM(II) COMPLEXES OF 8-THIOTHEOPHYLLINE - CRYSTAL-STRUCTURES OF [PT(MU-TT)(DPPM)](2)CENTER-DOT-2DMSO AND [(DPPM)PT(MU-TT)(2)PD(DPPM)]CENTER-DOT-7H(2)O/
E. Colacio et al., METAL-PURINE INTERACTIONS - HOMODINUCLEAR AND HETERODINUCLEAR PLATINUM(II) AND OR PALLADIUM(II) COMPLEXES OF 8-THIOTHEOPHYLLINE - CRYSTAL-STRUCTURES OF [PT(MU-TT)(DPPM)](2)CENTER-DOT-2DMSO AND [(DPPM)PT(MU-TT)(2)PD(DPPM)]CENTER-DOT-7H(2)O/, Inorganic chemistry, 36(8), 1997, pp. 1652-1656
The reaction of cis-[MCl(2)(dppm)] (M = Pt(II) and Pd(II); dppm = bis(
diphenylphosphino)methane) with H2TT and NaOH (H2TT = 8-thiotheophylli
ne) yields neutral mononuclear [M(HTT-S(8))(2)(dppm)] complexes. Homod
inuclear [M(mu-TT-N(7),S(8))(dppm)](2) (M = Pt(II) and Pd(II) are prep
ared either by the reaction of [M(HTT)(2)(dppm)] with cis-[MCl(2)(dppm
)] and NaOH or by the direct reaction of cis-[MCl(2)(dppm)] with Na2TT
, prepared in situ from H2TT and NaOH. The crystal structure of the Pt
derivative is reported: [Pt(mu-TT)(dppm)](2) . 2DMSO (3) crystallizes
in the triclinic space group <P(1)over bar> with a = 12.939(3) Angstr
om, b = 13.009(3) Angstrom, c = 22.980(5) Angstrom, alpha = 96.89(3)de
grees, beta = 103.53(3)degrees, gamma = 106.43(3)degrees, Z = 2, and R
(1) = 0.045. Heterodinuclear [(dppm)Pt(mu-TT)(2)Pd(L-L)] complexes are
obtained by reaction of [Pt(HTT)(2)(dppm)] with [PdCl2(L-L)] in basic
medium (L-L = dppm and 2,2'-bipyridine). The crystal structure of [(d
ppm)Pt(mu-TT)(2)Pd(dppm)]. 7H(2)O (5) is reported. The complex crystal
lizes in the orthorhombic space group P2(1)2(1)2(1) With a = 16.560(5)
Angstrom, b = 17.063(5) Angstrom, c = 24.428(5) Angstrom, Z = 4, and
R(1) = 0.042. The structures of 3 and 5 are almost identical, by which
5 can be seen as an isomorphic substitution of one of the Pt(II) ions
of 3 by a Pd(II) ion. The structures consist of dinuclear units havin
g a pseudo-2-fold axis perpendicular to that defined by the metal atom
s. The two metal atoms are bibridged by two mu-TT-N(7),S(8) ligands, i
n a head to tail arrangement. The square-planar coordination of the me
tal atoms is completed by a chelate dppm ligand. The steric repulsions
between the bulky dppm ligands must be the main factor precluding met
al-metal interaction in these compounds.