F. Fuge et al. / Journal of Organometallic Chemistry 694 (2009) 2395–2401
2399
J = 8.1 Hz, 2H, Ha), 7.26 (br. s, 1H, H6), 7.21 (d, J = 8.1 Hz, 2H, Hb),
6.99 (dd, J = 8.1/1.0 Hz, 1H, H4), 6.85 (d, J = 8.1 Hz, 1H, H3), 4.02
(q, J = 7.1 Hz, 2H, NCH2), 3.88 (q, J = 7.1 Hz, 2H, NCH2), 3.60 (s,
3H, NMe), 2.40 (s, 3H, MeAr), 2.36 (s, 3H, MeAr), 1.43 (t,
J = 7.1 Hz, 3H, CH2CH3), 1.27 (t, J = 7.1 Hz, 3H, CH2CH3). ES-MS (m/
z): 527.0708 [M+Na]+, 497.0730 [MꢀNO+Na]+. Anal. Calc. for
C21H26N4O2PdS (504.94): C, 46.95; H, 5.19; N, 11.10. Found: C,
46.94; H, 5.39; N, 11.05%. Crystals suitable for X-ray diffraction
were obtained by slow diffusion of Et2O into a CH2Cl2 solution of
the complex.
3.9. [Pd{
j
2C,N-4-MeC6H3N(Me)NO}{
j
2O,O-tBuC(O)CHC(O)tBu}] (8)
This was prepared as above from [Pd(
l
-O2CMe){j2C,N-4-
MeC6H3N(Me)NO}]2 (0.050 g, 0.079 mmol) and tBu2acac (34
lL).
0.049 g (70%) of a yellow solid was obtained. 1H NMR (400 MHz,
CDCl3, 25 °C): d = 7.52 (br. s, 1H, H6), 7.01 (dd, J = 8.1/1.0 Hz, 1H,
H4), 6.78 (d, J = 8.1 Hz, 1H, H3), 5.75 (s, 1H, CH), 3.51 (s, 3H,
t
t
NMe), 2.40 (s, 3H, MeAr), 1.26 (s, 9H, Bu), 1.23 (s, 9H, Bu). ES-
MS (m/z): 461.1031 [M+Na]+, 431.1047 [MꢀNO+Na]+. Anal. Calc.
for C19H28N2O3Pd (438.66): C, 52.00; H, 6.43; N, 6.38. Found: C,
51.70; H, 6.67; N, 6.03%.
3.5. [Pd{
MeC6H4C(O)NC(Se)NEt2)}] (4)
j j
2C,N-4-MeC6H3N(Me)NO}{ 2Se,O-4-
3.10. [Pd{
j
2C,N-4-MeC6H3N(Me)NO}(
j
2S,S-Et2NCS2)] (9)
2C,N-4-
This was prepared as above from [Pd(l-O2CMe){j
2C,N-4-
This was prepared as above from [Pd(l-O2CMe){j
MeC6H3N(Me)NO}]2 (0.050 g, 0.079 mmol) and Et2NCS2Na
(0.036 g, 0.159 mmol). 0.047 g (72%) of a yellow solid was ob-
tained. 1H NMR (400 MHz, CDCl3, 25 °C): d = 7.01 (br. s, 1H, H4),
6.99 (s, 1H, H6), 6.83 (d, J = 8.1 Hz, 1H, H3), 3.80–3.88 (m, 4H,
NCH2), 3.52 (s, 3H, NMe), 2.33 (s, 3H, MeAr), 1.35 (t, J = 7.1 Hz,
3H, CH2CH3), 1.30 (t, J = 7.1 Hz, 3H, CH2CH3). ES-MS (m/z):
425.9897 [M+Na]+, 395,9926 [MꢀNO+Na]+. Anal. Calc. for
C13H19N3OPdS2 (403.86): C, 38.66; H, 4.74; N, 10.40. Found: C,
38.65; H, 4.69; N, 10.53%. Slow diffusion of Et2O into a CH2Cl2 solu-
tion of the compound gave two types of crystals, which turned out
to be complex 9* and [Pd{j2S-S2CNEt2}2].
MeC6H3N(Me)NO}]2 (0.050 g, 0.079 mmol) and 4-MeC6H4-
C(O)NHC(Se)NEt2 (0.047 g, 0.158 mmol). 0.065 g (74%) of a yellow
solid was obtained. 1H NMR (400 MHz, CDCl3, 25 °C): d = 8.17 (d,
J = 8.1 Hz, 2H, Ha), 7.20 (d, J = 8.1 Hz, 2H, Hb), 7.15 (br. s, 1H, H6),
6.90 (dd, J = 8.1/1.0 Hz, 1H, H4), 6.84 (d, J = 8.1 Hz, 1H, H3), 4.03
(q, J = 7.1 Hz, 2H, NCH2), 3.87 (q, J = 7.1 Hz, 2H, NCH2), 3.60 (s,
3H, NMe), 2.39 (s, 3H, MeAr), 2.33 (s, 3H, MeAr), 1.44 (t,
J = 7.1 Hz, 3H, CH2CH3), 1.27 (t, J = 7.1 Hz, 3H, CH2CH3). ES-MS (m/
z): 575.0153 [M+Na]+, 553.0343 [M+H]+, 545.0175 [MꢀNO+Na]+.
Anal. Calc. for C21H26N4O2PdSe (551.84): C, 45.71; H, 4.75; N,
10.15. Found: C, 45.94; H, 4.74; N, 10.09%.
3.11. [Pd{j j
2C,N-4-MeC6H3N(Me)NO}( 2S,S-iPrOCS2)] (10)
3.6. [Pd{
C6H5C(O)NC(Se)NMePh)}] (5)
j j
2C,N-4-MeC6H3N(Me)NO}{ 2Se,O-
This was prepared as described above from [Pd(
l-
O2CMe){
j
2C,N-4-MeC6H3N(Me)NO}]2 (0.050 g, 0.079 mmol) and
This was prepared as above from [Pd(l-O2CMe){j
2C,N-4-
iPrOCS2K (0.028 g, 0.161 mmol). 0.050 g (81%) of a yellow solid
was obtained. 1H NMR (400 MHz, CDCl3, 25 °C): d = 7.04 (br. d,
J = 8.1 Hz, 1H, H4), 6.97 (br. s, 1H, H6), 6.86 (d, J = 8.1 Hz, 1H, H3),
5.65 (sept, J = 6.1 Hz, 1H, MeCH), 3.54 (s, 3H, NMe), 2.34 (s, 3H,
MeAr), 1.49 (d, J = 6.1 Hz, 6H, MeCH). ES-MS (m/z): 412.9586
[M+Na]+, 382.9604 [MꢀNO+Na]+. Anal. Calc. for C12H16N2O2PdS2
(390.82): C, 36.88; H, 4.13; N, 7.17. Found: C, 36.99; H, 4.36; N,
7.29%.
MeC6H3N(Me)NO}]2 (0.050 g, 0.079 mmol) and C6H5C(O)NHC-
(Se)NMePh (0.050 g, 0.159 mmol). 0.091 g (80%) of a yellow solid
was obtained. 1H NMR (400 MHz, CDCl3, 25 °C): d = 8.40 (m, 2H,
Ph), 7.29–7.55 (m, 8H, Ph), 6.93 (m, 1H, H6), 6.78–6.84 (m, 2H,
H3, H4), 3.72 (s, 3H, NMe), 3.59 (s, 3H, NMe), 2.23 (s, 3H, MeAr).
ES-MS (m/z): 594.9840 [M+Na]+, 573.0005 [M+H]+, 564.9858
[MꢀNO+Na]+. Anal. Calc. for C23H22N4O2PdSe (571.83): C, 48.31;
H, 3.88; N, 9.80. Found: C, 48.45; H, 3.59; N, 10.01%. Crystals suit-
able for X-ray diffraction were obtained by slow diffusion of Et2O
into a CH2Cl2 solution of the complex.
3.12. [Pd{
j
2C,N-4-MeC6H3N(Me)NO}{phen}]PF6 (11)
A
mixture of [Pd(l-O2CMe){j
2C,N-4-MeC6H3N(Me)NO}]2
3.7. [Pd{
j
2C,N-4-MeC6H3N(Me)NO}{
j
2O,O-MeC(O)CHC(O)Me}] (6)
(0.050 g, 0.079 mmol) and 1,10-phenanthroline (0.032 g,
0.161 mmol) in MeOH (15 mL) was refluxed for ca. 10 min. The ini-
tially orange solution turned yellow. Upon addition of 0.028 g
(0.172 mmol) NH4PF6 to the cold solution a bright yellow precipi-
tate formed. The solid was isolated by filtration and was washed
with H2O, MeOH and Et2O and was subsequently dried in air.
0.080 g (87%) of a yellow solid was obtained. 1H NMR (400 MHz,
This was prepared as above from [Pd(
MeC6H3N(Me)NO}]2 (0.050 g, 0.079 mmol) and acetylacetone
l
-O2CMe){
j
2C,N-4-
(20
l
L). 0.040 g (71%) of a yellow solid was obtained. 1H NMR
(400 MHz, CDCl3, 25 °C): d = 7.46 (d, J = 1.0 Hz, 1H, H6), 7.02 (dd,
J = 8.1/1.0 Hz, 1H, H4), 6.79 (d, J = 8.1 Hz, 1H, H3), 5.42 (s, 1H, CH),
3.52 (s, 3H, NMe), 2.40 (s, 3H, MeAr), 2.12 (s, 3H, MeC@O), 2.11
(s, 3H, MeC@O). ES-MS (m/z): 377.0087 [M+Na]+, 347.0111
[MꢀNO+Na]+. Anal. Calc. for C13H16N2O3Pd (354.70): C, 44.02; H,
4.55; N, 7.90. Found: C, 43.87; H, 4.38; N, 8.16%.
2
9
0
0
dmso-d6, 25 °C): d = 8.78 (dd, J = 5.0/1.0 Hz, 2H, H , H ), 8.59 (dd,
J = 8.0/1.0 Hz, 2H, H , H ), 8.08 (s, 2H, H , H ), 8.05 (dd, J = 8.0/
4
0
7
0
5
0
6
0
3
0
8
3
4
6
0
5.0 Hz, 2H, H , H ), 6.86–6.97 (m, 2H, H , H ), 6.72 (s, 1H, H ),
3.29 (s, 3H, NMe), 2.25 (s, 3H, MeAr). ES-MS (m/z): 435.0425
[M]+, 405.0439 [MꢀNO]+. Anal. Calc. for C20H17F6N4OPPd
(580.76): C, 41.36; H, 2.95; N, 9.65. Found: C, 41.71; H, 3.16; N,
9.94%.
3.8. [Pd{
j
2C,N-4-MeC6H3N(Me)NO}{
j
2O,O-CF3C(O)CHC(O)CF3}] (7)
This was prepared as above from [Pd(
MeC6H3N(Me)NO}]2 (0.050 g, 0.079 mmol) and hfacac (23 L).
l
-O2CMe){j2C,N-4-
3.13. [Pd{j
2C,N-4-MeC6H3N(Me)NO}{Me4phen}]PF6 (12)
l
0.063 g (86%) of a yellow solid was obtained. 1H NMR (400 MHz,
CDCl3, 25 °C): d = 7.25 (d, J = 1.5 Hz, 1H, H6), 7.06 (dd, J = 8.1/
1.5 Hz, 1H, H4), 6.79 (d, J = 8.1 Hz, 1H, H3), 6.12 (s, 1H, CH), 3.55
(s, 3H, NMe), 2.30 (s, 3H, MeAr). 19F NMR (376 MHz, CDCl3,
25 °C): d = ꢀ75.13, ꢀ75.77. Anal. Calc. for C13H16F6N2O3Pd
(462.64): C, 33.75; H, 2.18; N, 6.06. Found: C, 33.94; H, 2.02; N,
5.82%.
This was prepared as described above from [Pd(
O2CMe){
l-
j
2C,N-4-MeC6H3N(Me)NO}]2 (0.050 g, 0.079 mmol) and
3,4,7,8-tetramethyl-1,10-phenanthroline (0.038 g, 0.160 mmol).
0.092 g (91%) of a yellow solid was obtained. 1H NMR (400 MHz,
2
9
0
5
0
0
acetone-d6, 25 °C): d = 8.84 (br. s, 2H, H , H ), 8.25 (br. s, 2H, H ,
H ), 7.16–7.27 (m, 3H, H , H , H ), 3.57 (s, 3H, NMe), 2.83 (s, 6H,
6
0
3
4
6