A. Romerosa et al. / Inorganica Chimica Acta 353 (2003) 99Á
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105
vent. Single crystal structure determination of 1 was
carried out at 120 K from data collected using graphite
Pale yellow crystals of 1 were obtained from a
solution in EtOH/hexane (1:1) by slow evaporation at
room temperature.
monochromated Mo Ka radiation (lꢀ
/
0.71073) on a
Bruker SMART-CCD 1K detector diffractometer
equipped with a Cryostream N2 flow cooling device
[20]. Series of narrow v-scans (0.38) were performed at
several f-settings in such a way as to cover a sphere of
Yield 1: 86%, 1.87 gYield 2: 84%, 1.94 g;Yield 3: 64%,
1.52 g;Yield 4: 76%, 2.18 g.Melting point 1: 298Á
299 8C;Melting point 2: 312Á313 8C;Melting point 3:
253Á254 8C;Melting point 4: 261Á262 8C.
/
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/
˚
data to a maximum resolution of 0.70 A. Cell para-
meters were determined and refined using the SMART
software [21] from the centroid values of 625 reflections
with 2u values between 27 and 498. Raw frame data
were integrated using the SAINT program [22]. The
structure was solved using Direct Methods and refined
by full-matrix least-squares on F2 using SHELXTL [23].
No absorption correction was applied to the data.
The compound crystallizes in the orthorhombic
6.1. Synthesis of trans-[PdCl(PPh3)2LH] (Lꢀ
/
EBTT2ꢁ (5), PBTT2ꢁ (6))
By a similar procedure, 2 (0.46 g, 1 mmol) and 3 (0.47
g, 1 mmol) reacted with KOH (0.056 g, 1 mmol) and cis-
[PdCl2(PPh3)2] (0.70 g, 1 mmol) for 2 h in refluxed EtOH
(15 ml) to give rise the complexes 5 and 6 as red orange
precipitates, which were filtered out, washed with two
portions of cold EtOH and air dried.
system, space group Pbca, with aꢀ
/
12.447(4), bꢀ
/
3
˚
˚
13.585(5), cꢀ
Dcꢀ
1.630 g cmꢁ3 and mꢀ
tions were collected and 5175 unique reflections (Rint
0.0486) were used in all calculations (2umax 60.94, hꢀ
17Á16, kꢀ 18Á19, lꢀ 28Á29). From these, 3817
reflections were considered ‘observed’ (I ꢀ2s(I)). The
/
21.038(7) A, Uꢀ
/
3557(2) A , Zꢀ
/
8,
/
/
0.345 mmꢁ1. 41 294 reflec-
ꢀ
/
ꢀ
/
/
The complexes could be also obtained by previous
deprotonation of 2 (0.46 g, 1 mmol) and 3 (0.47 g, 1
mmol) with KOH (0.1 mol) in 15 ml of EtOH and, at
refluxed temperature, further reaction with PPh3 (0.2
mol) and Na2[PdCl4] (0.29 g, 1 mmol) dissolved in 3 ml
of H2O.
ꢁ
/
/
/
ꢁ
/
/
/
ꢁ
/
/
/
final wR (F2) was 0.1241 (all data) and the final R (F)
was 0.045 (observed data). All non-hydrogen atoms
were refined with anisotropic atomic displacement
parameters (adps). Hydrogen atoms were geometrically
placed and allowed to ride on their parent C atoms with
Yield 5: 44%, 0.49 g;Yield 6: 47%, 0.53 g.
Uiso (H)ꢀ/1.5 Ueq(C) for methyl H atoms, and 1.2
Ueq(C) for the methylene group. Idealized CÃ
/
H dis-
˚
tances were fixed at 0.98 and 0.99 A, respectively.
Hydrogen atoms bonded to N atoms were located
from a difference Fourier map and its coordinates and
isotropic adps were refined.
6.2. Synthesis of the complex trans-[(PdCl(PPh3)2)2L]
(Lꢀ
MBTT2ꢁ (7), EBTT2ꢁ (8), PBTT2ꢁ (9),
/
DBTT2ꢁ (10))
The complexes 7, 8, 9 and 10 were obtained by
reaction of the respective ligand 1 (0.43 g, 1 mmol), 2
(0.46, 1 mmol), 3 (0.47 g, 1 mmol) and 4 (0.53 g, 1 mmol)
with KOH (0.12 g, 2.2 mmol) and cis-[PdCl2(PPh3)2]
6. Preparation
Synthesis of bis(S-8-thiotheophylline)methane (MB-
TTH2) (1), 1,2-bis(S-8-thiotheophylline)ethane (EBT-
TH2) (2), 1,3-bis(S-8-thiotheophylline)propane (3),
1,10-bis(S-8-thiotheophylline)decane (DBTTH2) (4).
The ligands 1, 2, 3 and 4 were obtained by a similar
procedure. Into a suspension of potassium 8-thiotheo-
phyllinate in 20 ml of EtOH, which was generated in situ
by reaction of 8-thiotheophylline (1 g, 5 mmol) with
KOH (0.28 g, 5 mmol), the respective dibromoalkyl
(1.54 g, 2.2 mmol) (or PPh3 (1.15 g, 4.4 mmol)ꢂ
/
Na2[PdCl4] (0.64 g, 2.2 mmol) solved in 3 ml of H2O)
in 15 ml of refluxing EtOH. The orange-red precipitated
formed after 3 h was filtered out, washed with EtOH
(2ꢃ2 ml) and air dried.
/
The complexes 8, 9 were also obtained by refluxing
for 2 h the respective complexes 5 (1.12 g, 1 mmol) and 6
(1.13 g, 1 mmol) with KOH (0.056 g, 1 mmol) and cis-
[PdCl2(PPh3)2] (0.77, 1.1 mmol) (or PPh3 (0.58 g, 2.2
derivative, BrRBr (Rꢀ CH2 for 1, 1,2-(CH2)2 for 2,
/
Ã
/
mmol)ꢂ
/
Na2[PdCl4] (0.32 g, 1.1 mmol) solved in 3 ml of
red precipitated
1,3-(CH2)3 for 3, 1,10-(CH2)10 for 4), was added. The
mix was stirred for 30 min at room temperature and
then refluxed for 6 h. The yellow solution was slowly
H2O) in 10 ml of EtOH. The orangeÁ
/
obtained was isolated with a similar procedure that
described previously.
cooled and finally kept in a freezer all night. The whiteÁ
yellow powder precipitated was filtered out, washed
with H2O (2ꢃ2 ml), EtOH (2ꢃ2ml) and air dried.
/
Yield 7: 35%, 0.62 gYield 8: 65%, 1.16 g;Yield 9: 65%,
1.17 g;Yield 10: 40%, 0.76 g.
/
/
Romerosa, Antonio
