A. Klein et al. / Inorganica Chimica Acta 343 (2003) 189ꢂ
/
201
199
brownish residues. These were extracted with three
portions of 20 ml n-pentane and after careful filtration
of the combined solutions the solvent was distilled off
and the resulting solids were washed with n-pentane and
dried in vacuo. Further careful recrystallisation from
CH2Cl2 was required in cases where LiSbF6 had to be
removed from the product. Yields and analytical data
were given in Table 1. The complex [(COD)PdMe(OD)]
was prepared in the same way as the OH analogue by
adding KOD (40% in D2O).
1.95 (m, 2H, transNH2), 1.32 (d, 12H, cisCH3), 1.30 (d,
6H, transCH3), 0.26 (s, 3H, PdCH3). In the same way
141 mg (0.245 mmol, 66%) of the t-butylamino complex
11b was obtained. Anal. Calc. for C13H36F6N3Pd1Sb1:
C, 27.08; H, 6.29; N, 7.29; Pd, 18.45. Found: C, 27.05;
H, 6.20; N, 7.33; Pd, 18.15%. 1H NMR (THF-d8) d: 3.1
(m, 2H, transNH2), 2.46 (m, 4H, cisNH2), 1.35 (s, 18H,
cisCH3), 1.19 (s, 9H, transCH3), 0.59 (s, 3H, PdCH3).
3.8. Preparation of [(m-bpy){(bpy)PdMe}2](SbF6)2
(12)
3.5. Preparation of [(COD)PdMe(Meꢀ
/
pz)](PF6)2
(8)
To a solution of 200 mg (0.372 mmol) THF complex
in 50 ml of THF 139 mg of 2,2?-bipyridine were added.
The colourless solution turned yellow and showed
precipitation. After stirring for 3 h the fine yellow
precipitate, that had formed, was collected, washed
with three 10 ml portions of Et2O and dried in vacuo.
Yield: 169 mg (0.142 mmol, 75%). Anal. Calc. for
C32H30F12N6Pd2Sb2: C, 32.49; H, 2.56; N, 7.10; Pd,
17.99. Found: C, 32.68; H, 2.44; N, 6.89; Pd, 18.26%. 1H
NMR (acetone-d6) d: 9.6 (d, 1H, H6), 8.94 (d, 2H,
mH6ƒ6§); 8.9 (d, 2H, H3), 8.88 (d, 2H, H3?), 8.80 (d, 2H,
H6?), 8.55 (d, 2H, mH3ƒ3§); 8.40 (m, 2H, H4), 8.30 (m,
2H, mH4ƒ; H4§); 7.83 (m, 2H, H5), 7.78 (m, 2H, H5ƒ5§);
7.70 (m, 2H, H5?). 0.60 (s, 6H, Me). CV in DMF:
To a solution of 300 mg (0.67 mmol) of the THF
complex [(COD)PdMe(THF)](PF6) in 50 ml of THF 161
mg (0.67 mmol) of N-methyl-pyrazinium hexafluoro-
phosphate (Meꢀ/pz)(PF6), were added and the solution
stirred for 3 h. After removal of all volatiles the greenish
yellow residue was extracted with 25 ml of acetone and
carefully filtrated. After evaporation to dryness a light
yellow solid was obtained that was dried in vacuo.
Yield: 216 mg (0.35 mmol, 52%). Anal. Calc. for
C14H22F12N2P2Pd1: C, 27.36; H, 3.61; N, 4.56; Pd,
17.31. Found: C, 26.81; H, 3.62; N, 4.44; Pd, 18.23%.
1H NMR (acetone-d6) see Table 2. CV in THF:
E(1)1/2
(irr.).
ꢁ
/
ꢃ
/
0.70 V (DEpp
ꢁ
/
73 mV): E(2)pcꢁ
/
ꢃ1.45 V
/
E(1)pa
E(3)1/2
ꢁ
/
0.66 V (irr.), E(2)1/2
ꢁ
/
ꢃ
ꢁ
/
1.34 V (63 mV),
ꢁ
/
ꢃ
/
1.62 V (75 mV), E(4)1/2
/
ꢃ
/
1.91 V (67 mV).
3.6. Preparation of [(py)3PdMe](SbF6) (9)
3.9. 1H NMR data of [(bpy)PdMe(THF)]ꢀ
The preparation was afforded like described for
[(COD)PdMe(py)](SbF6)] but 5 equiv. of Py were added.
Recrystallisation of a brownish oily residue from
CH2Cl2 afforded colourless microcrystals. Yield: 153
In acetone-d6 d: 9.60 (d, 1H, H6), 8.52 (ddd, 1H, H4),
8.40 (d, 1H, H6?), 8.25 (d, 1H, H3), 8.15 (d, 1H, H3?),
8.02 (ddd, 1H, H5), 7.80 (ddd, 1H, H4?), 7.10 (ddd, 1H,
H5?), 3.6 (m, 4H, THFa), 1.79 (m, 4H, THFb), 0.45 (s,
3H, Me).
mg
(0.26
mmol,
68%).
Anal.
Calc.
for
C16H18F6N3Pd1Sb1: C, 32.33; H, 3.05; N, 7.07; Pd,
17.90. Found: C, 32.31; H, 2.96; N, 6.94; Pd, 17.78%. 1H
NMR (THF-d8) d: 8.82 (m, 4H, cisPy2,6), 8.58 (m, 2H,
3.10. EXAFS measurements
transPy2,6), 7.96 (tt, 2H, cisPy4, 3JHHꢁ
/
8.95 Hz,
7.56
4JHHꢁ1.6 Hz), 7.82 (t, 1H, transPy4, 3JHHꢁ
Hz), 7.51 (m, 4H, cisPy2,5), 7.42 (m, 2H, transPy2,5),
/
/
The EXAFS measurements of 1, 2, 6 and 7 were
performed at the palladium K-edge (24 350 eV) at the
¨
beamline X1.1 (ROMO II) of the Hamburger Synchro-
0.69 (s, 3H, PdCH3).
tronstrahlungslabor (HASYLAB) at DESY, Hamburg
under ambient conditions. The synchrotron beam cur-
rent was between 80 and 140 mA (positron energy 4.45
GeV). For harmonic rejection, the second crystal of the
Si(311) double crystal monochromator was tilted to
30%. Data were collected in transmission mode with ion
chambers flushed with Ar. The energy was calibrated
with a Pd metal foil of 5 mm thickness. The samples
themselves were embedded in a polyethylene matrix and
pressed to pellets of 1.3 cm diameter. The concentration
of all samples were adjusted to yield an absorption jump
3.7. Preparation of [(R?NH2)3PdMe](SbF6) (R?ꢁ
(11a), t-Bu (11b))
/
i-Pr
The preparation was carried out as described for
[(COD)PdMe(L)](SbF6)] LꢁPy, Col etc. but 5 equiv. of
/
the trialkylamine were added. After workup 119 mg
(0.223 mmol or 60%) of the i-propylamino complex 11a
was isolated. Anal. Calc. for C10H30F6N3Pd1Sb1: C,
22.47; H, 5.66; N, 7.86; Pd, 19.91. Found: C, 23.52; H,
1
5.83; N, 7.79; Pd, 20.34%. H NMR (CD2Cl2) d: 2.99
3
(sept, 2H, cisNCH, JHHꢁ
/
6.63 Hz), 2.84 (sept, 1H,
transNCH, 3JHHꢁ
6.18 Hz), 2.41 (m, 4H, cisNH2),
of dmd :/1.5. EXAFS data were analysed with a
/
program package developed for the investigation of