A. Zucca et al. / Journal of Organometallic Chemistry 694 (2009) 3753–3761
3759
were recorded with a FT-IR Jasco 480P using nujol mulls. 1H and
31P NMR spectra were recorded with a Varian VXR 300 spectrom-
eter operating at 300.0 and 121.4 MHz, respectively. Chemical
shifts are given in ppm relative to internal TMS (1H) and external
6.62 (td, 1H, JH–H = 8.1 Hz); 6.98–7.62 (m, 23H, aromatics); 7.86
(dd, 1H,JH–H = 8.1 Hz); 8.32 (m, 2H); 8.55 (dd, 1H, JH–H = 8.4 Hz);
8.75 (dd, 1H, JH–H = 8.1 Hz). 31P NMR (CDCl3):
d
20.05 ppm,
1JPt–P = 4262 Hz. IR (Nujol,
t
max/cmꢀ1): 1060 s, broad (BFꢀ4 ).
85% H3PO4 (
31P), J values are given in Hz. The H–H 2D COSY spec-
trum was performed by means of a standard pulse sequence. Con-
ductivities were measured with a Philips PW 9505 conductimeter.
4.1.5. Synthesis of [Pd(L–H)(CO)][BF4] (8)
AgBF4 (38.9 mg, 0.20 mmol) was added under vigorous stirring
to an acetone solution of 2 (60 mL, 0.20 mmol). The precipitate
formed (AgCl) was filtered off and CO was bubbled into the solu-
tion at room temperature for 2 h. Then the solution was concen-
trated to dryness to give a crude product. Crystallisation of
compound 8 from the crude of from the reaction solution produced
partial decomposition. Yield: 60%. 1H NMR (CDCl3): d 7.02 (dd, 1H,
JH–H = 7.9 Hz); 7.12 (dt, 1H, JH–H = 7.5 Hz, JH–H = 1.5 Hz); 7.28 (m,
1H, partially overlapping with the solvent); 7.54–7.68 (m, 7H),
4.1. Preparations
4.1.1. Synthesis of [Pt(L–H)Cl] (1)
To a solution of K2[PtCl4] (306.5 mg, 0.74 mmol) in H2O (10 mL)
were added, under vigorous stirring, 250 mg of L (0.81 mmol) and
3.7 mL of 2 N HCl. The mixture was heated to reflux for 5 days, then
it was cooled and the precipitate formed was filtered off and
washed with water, ethanol and diethyl ether. The crude product
was recrystallised from dichloromethane/diethyl ether to give
the analytical sample as an orange solid. Yield: 50%. Mp: >260 °C.
Anal. Calc. for C22H15 ClN2Pt: C, 49.12; H, 2.81; N, 5.21. Found: C,
7.77 (dd, 1H, JH–H = 7.0 Hz, JH–H = 1.6 Hz); 8.30 (t, 1H, JH–H
8.0 Hz); 8.39 (t, 1H, JH–H = 8.0 Hz); 8.46 (d, 1H, JH–H = 8.1 Hz);
8.71 (dd, 1H, JH–H = 8.2 Hz). IR (CHCl3,
max/cmꢀ1): 2130s; (Nujol,
max/cmꢀ1): 2135s, 1060s, broad (BFꢀ4 ).
=
t
t
49.37; H, 2.94; N, 4.93%. 1H NMR (CDCl3): d 7.07 (td, 1H, JH–H
=
=
00
6.6 Hz, JH–H = 0.9 Hz, H5 ); 7.13 (td, 1H, JH–H = 7.9 Hz, JH–H
4.1.6. Synthesis of [Pd(L–H)(PPh3)][BF4] (9)
00
00
1.3 Hz, H4 ); 7.33 (dd, 1H, H6 ); 7.50 (dd partially overlapping,
AgBF4 (38.9 mg, 0.20 mmol) was added under vigorous stirring
to an acetone solution of 2 (60 mL, 0.20 mmol). The precipitate
formed (AgCl) was filtered off and solid PPh3 (1:1 molar ratio)
was added to the filtered solution. The solution was stirred at room
temperature for 1 h, then it was concentrated to a small volume
and treated with diethyl ether. The precipitate formed was filtered
off and washed with diethyl ether to give the analytical sample.
Yield: 88%. Mp: 235–240 °C (dec). Anal. Calc. for C40H30BF4N2PPd:
C, 62.98; H, 3.96; N, 3.67. Found: C, 62.84; H, 3.91; N, 3.55. 1H
1H, H5), 7.53 (m, 3H, Hm + Hp PPh3); 7.65 (dd, 1H, JH–H = 7.0 Hz,
H3); 7.70 (m, 2H, Ho PPh3); 7.72 (partially overlapping, 1H, H5 );
7.77 (dd, 1H, H3 ); 7.86 (t, 1H, JH–H = 8.1 Hz, H4); 7.95 (dd, 1H,
JH–H = 7.8 Hz, JH–H = 1.3 Hz, H3 ); 8.05 (t, 1H, JH–H = 7.7 Hz, H4 ).
0
00
0
0
Assignments are based on a 2D COSY spectrum.
4.1.2. Synthesis of [Pd(L–H)Cl] (2)
Complex 2 was obtained following the same procedure of com-
plex 1, using Na2[PdCl4] instead of K2[PtCl4]. Yield: 46%. Mp:
>260 °C. Anal. Calc. for C22H15ClN2Pd: C, 58.82; H, 3.37; N, 6.24.
Found: C, 58.46; H, 3.19; N, 6.07%. 1H NMR (CDCl3): d 7.04–7.09
NMR (CDCl3): d 6.39 (d, 1H, JH–H = 7.8 Hz); 6.67 (dt, 1H, JH–H
7.8 Hz, JH–H = 1.7 Hz); 7.09–7.32 (m, 18H); 7.41–7.48 (m, 4H),
7.63 (dd, 1H, JH–H = 7.8 Hz, JH–H = 1.6 Hz); 7.89 (d, 1H, JH–H
=
=
00
(m, 2H, Hmeta); 7.33 (m, 1H, H6 ); 7.52–7.58 (m, 4H, aromatics);
8.0 Hz); 8.26 (t, 1H, JH–H = 7.9 Hz); 8.32 (t, 1H, JH–H = 7.9 Hz); 8.49
7.61 (m, 1H, H3 ); 7.70–7.78 (m, 3H, aromatics); 7.82–7.90 (m,
(d, 1H, JH–H = 7.8 Hz); 8.65 (d, 1H, JH–H = 7.8 Hz). 31P NMR (CDCl3):
00
2H, aromatics); 7.95–8.00 (m, 2H, H4, H3 or H4 , H3 ).
Compounds [Pt(L0–H)Cl] and [Pd(L0–H)Cl] can be obtained in a
similar way from L0 instead of L.
d 33.25 ppm. IR (Nujol, t
max/cmꢀ1): 1090s, 1060s, broad (BFꢀ4 ).
0
0
4.1.7. Synthesis of [Pd(L0–H)(CO)][BF4] (10)
AgBF4 (39.0 mg, 0.20 mmol) was added under vigorous stirring
to an acetone solution of [Pd(L0–H)Cl] (60 mL, 0.20 mmol). The pre-
cipitate formed (AgCl) was filtered off and CO was bubbled into the
solution at room temperature for 2 h. The precipitate formed was
filtered off and washed with CH2Cl2 to give the analytical sample
4.1.3. Synthesis of [Pt(L–H)(CO)][BF4] (6)
AgBF4 (21.4 mg, 0.11 mmol) was added under vigorous stirring
to an acetone solution of 1 (20 mL, 60 mg, 0.11 mmol). The precip-
itate formed (AgCl) was filtered off and CO was bubbled into the
solution at room temperature for 12 h. Then the solution was con-
centrated to a small volume and treated with n-hexane. The pre-
cipitate formed was filtered off and washed with n-hexane to
give the analytical sample. Yield: 60%. Mp: 120 °C. Anal. Calc. for
C23H15BF4N2OPt: C, 44.75; H, 2.45; N, 4.54. Found: C, 44.47; H,
2.41; N, 4.52%. 1H NMR (CDCl3): d 7.09–7.19 (m, 2H, aromatics);
7.50–7.65 (m, 7H, aromatics); 7.78 (d, 1H, JH–H = 8.0 Hz, aromatics);
7.86 (d, 1H, JH–H = 7.8 Hz, aromatics); 8.27 (t, 1H, JH–H = 8.0 Hz, H4
as
a yellow solid. Yield 92%. Mp: 200 °C. Anal. Calc. for
C17H11N2BF4OPd: C, 45.12; H, 2.45; N, 6.19. Found: C, 44.56; H,
2.27; N, 5.84. IR (Nujol,
(BFꢀ4 ).
t
max/cmꢀ1): 2130s (CO), 1060 s, broad
4.1.8. Synthesis of [Pt(L–H)H] (11)
To a solution of 1 (135 mg, 0.25 mmol) in anhydrous THF
(90 mL) was added, under argon, NaBH4 (29.1 mg, 0.77 mmol).
The mixture was stirred at room temperature for 3 h, then it was
filtered and the resulting solution was concentrated to a small vol-
ume. Addition of n-pentane produced a precipitate that was fil-
tered off and washed with n-pentane to give the analytical
sample as a red solid. Yield: 73 mg, 58%. Mp: 176 °C. Anal. Calc.
for C22H16N2Pt: C, 52.48; H, 3.20; N, 5.56. Found: C, 52.26; H,
0
0
0
or H4 ); 8.42–8.51 (m, 2H, H5 or H5 , H4, or H4 ); 8.76 (d, 1H,
0
JH–H = 7.1 Hz, H5 or H5 ). IR (Nujol,
t
max/cmꢀ1): 2108s (CO), 1066s,
broad (BFÞꢀ4 ).
4.1.4. Synthesis of [Pt(L–H)(PPh3)][BF4] (7)
AgBF4 (42.8 mg, 0.22 mmol) was added under vigorous stirring
to an acetone solution of 1 (20 mL, 120 mg, 0.11 mmol). The pre-
cipitate formed (AgCl) was filtered off and solid PPh3 (1:1 molar ra-
tio) was added to the filtered solution. The solution was stirred at
room temperature for 3 h, then it was concentrated to a small vol-
ume and treated with n-hexane. The precipitate formed was fil-
tered off and washed with n-hexane to give the analytical
2.99; N, 5.25. 1H NMR (CD3)2CO: d ꢀ10.67 (s, broad, 1H, JPt–H
=
1504 Hz, Pt–H); 6.94–6.88 (m, 2H, aromatics); 7.53–7.41 (m, 5H,
aromatics); 7.96–7.79 (m, 4H, aromatics); 8.17–8.04 (m, 2H, aro-
matics); 8.38–8.31 (m, 2H, aromatics). IR (Nujol, t
max/cmꢀ1): 2114.
4.1.9. Reaction of [Pt(L–2H)(DMSO)], compound G, with HCl
To a solution of [Pt(L–2H)(DMSO)] (85 mg, 0.14 mmol) in ace-
tone (40 mL) were added 1.4 mL of 0.1 N HCl and a few drops of
DMSO. The mixture was stirred at room temperature for 3 h, then
sample.
Yield:
90%.
Mp:
189 °C.
Anal.
Calc.
for
C40H30BF4N2PPtꢁ3H2O: C, 53.05; H, 4.01; N, 3.09. Found: C, 52.96;
H, 3.97; N, 3.44%. 1H NMR (CDCl3): d 6.39 (dd, 1H, JH–H = 7.1 Hz);