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D. Aguilar et al. / Journal of Organometallic Chemistry 693 (2008) 417–424
(2.78 g, 92.4%) [67]. In the second step, the phosphonium 4
(1.00 g, 2.51 mmol) reacts with Na2CO3 (0.27 g,
2.51 mmol) in MeOH/H2O (1/7, 80 ml), giving 5 as a white
solid. Yield: 0.45 g (56.7%). Selected spectroscopic data: IR
maj.), 7.83 (m, Ho, PPh, maj.), 7.99 (m, Ho, PPh, min),
3
8.06 (d, JHH = 7.2, Ho, PhC(O), min), 8.10 (d,
3JHH = 7.2, Ho, PhC(O), maj.). 13C{1H} NMR (CDCl3):
1
d = 11.94 (d, PMe, maj., JPC = 52.3), 14.00 (d, PMe,
(m, cmꢀ1): 1504 (mCO). H NMR (CDCl3): d = 2.35 (d, 3H,
min, 1JPC = 62.2), 27.61 (Me, acac, maj.), 27.84 (Me, acac,
1
2JPH = 14.0, PMe), 4.14 (s, br, 1H, PCH), 7.2-7.29 (m, 3H,
min), 27.97 (Me, acac, maj.), 28.02 (Me, acac, min), 30.78
1
Hm, Hp, PhC(O)), 7.42 (m, 4H, Hm, PPh2), 7.48 (td, 2H, Hp,
(d, CHP, maj., JPC = 63.0), 35.14 (d, CHP, min,
3
4
PPh2, JHH = 6.8, JHH = 1.2), 7.63 (dd, 4H, Ho, PPh2,
1JPC = 62.8), 99.45 (CH, acac, maj.), 99.57 (CH, acac,
3JPH = 12.4, JHH = 6.8), 7.87 (dd, 2H, Ho, PhC(O)).
min), 124.40 (d, C5, C6H4, min, JPC = 13.5), 124.75 (d,
3
4
31P{1H} NMR (CDCl3): d = 10.82.
C5, C6H4, maj., JPC = 13.3), 125.31 (d, Ci, PPh, min,
4
3
1JPC = 67.9), 128.29 (d, C6, C6H4, maj., JPC = 16.6),
4.2.5. Synthesis of [Pd(l-Cl){C6H4(PPh(Me)CHC(O)
Ph-j-C,C)-2}]2(6)
128.64 (d, C6, C6H4, min, 4JPC = 16.4), 127.51 (Cm, PhCO,
min), 127.62 (Cm, PhCO, maj.), 127.31 (d, Ci, PPh, maj.,
4
To a solution of 5 (1.000 g, 3.14 mmol) in CH2Cl2 (10 ml),
Pd(OAc)2 (0.710 g, 3.14 mmol) was added, and the resulting
mixture was refluxed with vigorous stirring for 24 h. After the
reaction time, the solvent was evaporated and the yellow
solid residue was dissolved in 15 ml of MeOH and anhydrous
LiCl (0.130 g, 3.140 mmol) was added. Immediately a yellow
solid (6) precipitated. The stirring was maintained during
30 min at room temperature and the resulting suspension
was filtered. The yellow solid was washed with MeOH
(10 ml) and Et2O (50 ml) and air dried. 6 was characterized
(NMR) as a mixture of eight diastereoisomers with a molar
ratio 1.00/0.59/0.67/2.23/3.47/1.34/0.98/0.43. Yield: 1.380 g
(95.7%). Complex 6 was recrystallized from CH2Cl2/OEt2,
giving crystals of 6.CH2Cl2, which were used for analytical
1JPC = 77.1), 128.63 (d, Co, PhCO, maj., JPC = 1.4),
4
128.84 (d, Co, PhCO, min, JPC = 1.4), 128.94 (d, Cm,
3
PPh, min, JPC = 11.2), 129.41 (d, Cm, PPh, maj.,
3
3JPC = 11.2), 130.23 (d, C4, C6H4, min, JPC = 3.4),
3
130.38 (d, C4, C6H4, maj., JPC = 3.4), 131.56 (d, Co,
2
PPh, maj., JPC = 9.3), 131.63 (Cp, PhCO, min), 131.81
4
(Cp, PhCO, maj.), 132.60 (d, Cp, PPh, maj., JPC = 2.8),
4
132.76 (d, Cp, PPh, min, JPC = 2.8), 133.01 (d, Co, PPh,
min, 2JPC = 9.4), 133.72 (d, C3, C6H4, maj.,
2JPC = 15.1 Hz), 138.07 (d, Ci, PhCO, min, 3JPC = 5.2 Hz),
1
138.34 (d, C2,, C6H4, min, JPC = 115.7), 138.48 (d, Ci,
3
PhCO, maj, JPC = 8.1 Hz), 138.69 (d, C2, C6H4, maj.,
2
1JPC = 103.9), 157.99 (d, C1, C6H4, min, JPC = 22.1),
2
158.34 (d, C1, C6H4, maj., JPC = 20.6), 186.04 (CO, acac,
purposes. Anal. Calc. C42H36Cl2O2P2PdÅ CH2Cl2 (1003.3):
maj.), 186.51 (CO, acac, min), 186.79 (CO, acac, min),
186.89 (CO, acac, maj.), 195.00 (d, CO, ylide, min.
2
C, 51.47; H, 3.82. Found: C, 51.52; H, 3.61. MS (MALDI+):
m/z (%) = 881 (50) [MꢀCl]+. IR (m, cmꢀ1): 1614
(mCO).31P{1H} NMR (CDCl3): d = 15.91, 16.12, 17.23,
18.12, 18.95, 19.11, 19.69, 19.90.
2
2JPC = 4.6), 198.59 (d, CO, ylide, maj., JPC = 3.9).
31P{1H} NMR (CDCl3): d = 19.21 (C6H4-2-PPhMe, min),
21.43 (C6H4-2-PPhMe, maj.).
4.2.6. Synthesis of [Pd(acac-O,O0){C6H4(PPh(Me)CHC
(O)Ph-j-C,C)-2}] (7)
4.2.7. Synthesis of [PdCl{C6H4(PPh(Me)CHC(O)Ph-j-
C,C)-2}PPh3] (8)
Complex 7 was prepared following an experimental
method similar to that described for 3, but using 6 as start-
ing compound. Thus, 6 (0.150 g, 0.16 mmol) was reacted
with Tl (acac) (0.100 g, 0.33 mmol), giving 7 as a yellow
solid, which was characterized as a mixture of two diaste-
reoisomers in 5/1 molar ratio (d.e. = 66.7%). Yield:
0.110 g (61.5%). Anal. Calc. for C26H25O3PPd (522.9): C,
59.21; H, 4.82. Found: C, 58.91; H, 4.93%. MS
(MALDI+): m/z (%) = 523 (55) [M]+. IR (m, cmꢀ1): 1625
Solid PPh3 (0.086 g, 0.33 mmol) was added to a suspen-
sion of 6 (0.150 g, 0.16 mmol) in 5 ml of CH2Cl2. The initial
suspension gradually dissolved and, after 30 min stirring at
r.t., a pale yellow solution was obtained. After the reaction
time, any remaining insoluble material was filtered over
Celite and discarded. The resulting solution was evapo-
rated to dryness and the oily residue was treated with
20 ml of Et2O, giving 8 as a white solid. The solid was char-
acterized (NMR) as a mixture of diastereoisomers in 7/1
molar ratio (d.e. = 75%). Yield: 0.092 g (77%). Anal. Calc.
C39H33ClOP2Pd (721.6): C, 64.92; H, 4.61. Found: C,
64.88; H, 4.55%. MS (MALDI+): m/z (%) = 686 (100)
1
(mCO, ylide), 1564 (mCO, acac), 1514 (mCO, acac). H NMR
(CDCl3): d = 1.53 (s, Me, acac, maj.), 1.75 (s, Me, acac,
min), 1.91 (s, Me, acac, maj.), 1.94 (s, Me, acac, min),
2
2
1
2.45 (d, JPH = 12.6, PMe, min), 2.48 (d, JPH = 13.2,
[MꢀCl]+. IR (m, cmꢀ1): 1615 (mCO). H NMR (CDCl3):
2
PMe, maj.), 4.46 (d, JPH = 2.4, CHP, maj.), 4.50 (d,
d = 2.20 (d, 2JPH = 12.4, PMe, maj.), 2.54 (d,
2JPH = 12.6, PMe, min), 5.01 (m, CHP, min), 5.20 (dd,
2JPH = 4.8, CHP, min), 5.11 (s, CH, acac, maj.), 5.17 (s,
CH, acac, min), 6.98–7.09 (m, H6 and H5, C6H4, both),
7.17–7.21 (m, H4, C6H4, both), 7.24 (m, Hm, PhC(O),
3
2JPH = 7.6, JPH = 6.8, CHP, maj.), 6.11–6.25 (m, H6 and
H5, C6H4, min), 6.35 (m, H6, C6H4, maj.), 6.43 (t,
3
min), 7.28 (t, JHH = 7.3, Hm, PhC(O), maj.), 7.34 (t,
3JHH = 7.6, H5, C6H4, maj.), 6.77 (m, H4, C6H4, min),
3JHH = 7.3, Hp, PhC(O), min), 7.38 (t, JHH = 7.2, Hp,
6.85 (td, JPH = 4.8, JHH = 7.0, H4, C6H4, maj.), 7.10
3
4
3
3
4
PhC(O), maj.), 7.45–7.49 (m, Hm, PPh, both), 7.52–7.56
(td, JHH = 3JHH = 7.4, JPH = 1.6, Hm, PPh3, maj.),
7.16–7.18 (m, H3, C6H4, both, Hm, PPh3, min), 7.22 (t,
Hp, PPh3, both), 7.27–7.37 (m, Ho, PPh3, maj., Hm,
3
4
(m, Hp, PPh, both), 7.66 (dd, JHH = 7.8, JHH = 2.6, H3,
C6H4, min), 7.68 (dd,3JHH = 7.4, JHH = 2.1, H3, C6H4,
4