J.H. Groen et al. / Journal of Organometallic Chemistry 573 (1999) 3–13
5
BIAN)2]SO3CF3 (1a) as a brown solid compound
(130.4 mg, 95%).
4.00 (s, H12), 2.6 (4H, m, CH2P), 1.95 (2H, m,
CH2CH2P), 0.38 (dd, J=6.5, 3.2 Hz, MeꢀPd). 31P-
NMR (CDCl3): l 23.6 (d, J=53 Hz, P cis to Me),
−2.0 (d, J=53 Hz, P trans to Me). Mass found:
m/z=925.2283. [C54H49N2O2P2Pd]+ calc.: m/z=
925.2323.
Complexes 2a–5a could be synthesized from
[Pd(Me)(NCMe)(p-An-BIAN)]SO3CF3 and LꢀL or
from [Pd(Me)(NCMe)(LꢀL)]SO3CF3 and p-An-BIAN
in the same way (81–93%). No correct microanalyses
were obtained for 2a–5a due to the presence of a
small amount (5–10%) of [Pd(Me)(LꢀL)2]SO3CF3 or
other unidentified impurities.
2.3. Synthesis of [Pd(C(O)Me)(p-An-BIAN)(LꢀL)]SO3-
CF3 (LꢀL=p-An-BIAN (1b), phen (2b))
1
1a: H-NMR (CDCl3): l 8.08 (d, J=8.3 Hz, H5),
7.50 (pst, H4), 7.0 (20H, m, H3, H9, H10), 3.89 (s,
H12), 0.70 (s, PdꢀMe). 13C-NMR (CDCl3): l 166.9
(C1), 159.4 (C11), 143.5 (C7), 140.8 (C8), 131.6 (C5),
131.6 (C6), 128.9 (C4), 127.2 (C2), 125.2 (C3), 122.4
(C10), 115.5 (C9), 56.2 (C12), 7.1 (PdꢀMe). 15N-NMR
A solution of [Pd(Me)(p-An-BIAN)2]SO3CF3 (1a)
(39.4 mg, 0.037 mmol) in 20 ml of dichloromethane
was stirred at 20°C in a CO atmosphere. After 10
min, the solution was filtered through Celite and the
residue was extracted with dichoromethane (5 ml).
The combined filtrates were evaporated to dryness
and the product was washed with hexane (2×20 ml),
yielding 1b as a dark brown solid (34.3 mg, 85%).
Complex 2b was synthesized from 2a in the same
way (73%).
(CDCl3):
l −97.1. Mass found: m/z=905.2319.
[C53H43N4O4Pd]+ calc.: m/z=905.2239. Anal. Found:
C, 61.23; H, 4.07; N, 5.33. C54H43F3N4O7PdS calc.: C,
61.45; H, 4.11; N, 5.31.
1
2a: H-NMR (CDCl3): l 8.82 (dd, J=5.1, 1.2 Hz,
H13), 8.55 (dd, J=8.3, 1.2 Hz, H15), 8.06 (d, J=8.3
Hz, H5), 7.96 (dd, J=8.3, 5.1 Hz, H14), 7.90 (s,
H18), 7.51 (pst, H4), 7.13 (6H, m, H3, H10), 6.98 (d,
J=8.9 Hz, H9), 3.82 (s, H12), 1.06 (s, PdꢀMe). 13C-
NMR (CDCl3): l 162.9 (C1), 158.3 (C11), 148.4
(C13), 145.5 (C17), 142.4 (C8), 141.2 (C7), 138.5
(C15), 130.9 (C6), 130.4 (C5), 130.0, 127.9, 127.9,
125.7 (C2, C14, C16, C18), 127.3 (C4), 124.5 (C3),
120.9 (C10), 115.0 (C9), 55.4 (C12), 2.1 (PdꢀMe). 15N-
NMR (CDCl3): l −79.7 (BIAN nitrogen atoms),
−138.0 (phen nitrogen atoms). Mass found: m/z=
693.1443. [C39H31N4O2Pd]+ calc.: m/z=693.1482.
1
1b: H-NMR (CDCl3): l 8.09 (d, J=8.3 Hz, H5),
7.52 (pst, H4), 7.20 (d, J=8.9 Hz, H10), 7.15 (d,
J=7.3 Hz, H3), 6.89 (d, J=8.9 Hz, H9), 3.80 (s,
H12), 1.89 (s, C(O)Me). 13C-NMR (CDCl3): l 221.4
(CO), 165.1 (C1), 158.9 (C11), 142.8 (C7), 139.9 (C8),
131.0 (C5), 131.0 (C6), 128.2 (C4), 126.6 (C2), 124.5
(C3), 122.1 (C10), 114.9 (C9), 55.4 (C12), 30.3
(C(O)Me). IR (KBr): 1708 cm−1, w(CO). Mass found:
m/z=933.2246. [C54H43N4O5Pd]+
calc.: m/z=
933.2268. Anal. Found: C, 61.09; H, 3.95; N, 5.23.
C55H43F3N4O8PdS calc.: C, 60.97; H, 4.00; N, 5.17.
1
1
3a: H-NMR (CDCl3): l 8.31 (d, J=8.2 Hz, H15),
2b: H-NMR (CDCl3): l 8.70 (d, J=5.0 Hz, H13),
8.11 (d, J=8.4 Hz, H5), 7.79 (s, H18), 7.76 (d, J=
8.2 Hz, H14), 7.49 (pst, H4), 7.01 (2 H, br, H3), 6.8
(8H, br, H9, H10), 3.80 (6H, br, H12), 3.35 (s, H19),
0.61 (s, PdꢀMe). 13C-NMR (CDCl3): l 159.0 (C13),
158.6 (C11), 144.4 (C17), 141.8 (C8), 137.7 (C15),
131.3 (C16), 131.0 (C5), 128.5 (C4), 127.7 (C2), 125.9
(C3), 124.9, 124.6 (C14, C18), 121.6 (br, C10), 114.4
(br, C9), 55.4 (C12), 28.0 (C19), 2.4 (PdꢀMe), signals
of C1, C6, and C7 were not observed. 15N-NMR
(CDCl3): l −114.0 (dmphen nitrogen atoms), signals
of BIAN nitrogen atoms were not observed. Mass
found: m/z=721.1770. [C41H35N4O2Pd]+ calc.: m/z=
721.1795.
8.60 (d, J=8.2 Hz, H15), 8.10 (d, J=8.3 Hz, H5),
7.98 (s, H18), 7.94 (dd, J=8.2, 5.0 Hz, H14), 7.54
(pst, H4), 7.15 (d, J=7.4 Hz, H3), 7.01 (d, J=8.9
Hz, H10), 6.94 (d, J=8.9 Hz, H9), 3.83 (s, H12),
2.57 (s, C(O)Me). 13C-NMR (CDCl3): l 229.8 (CO),
163.4 (C1), 158.5 (C11), 149.6 (C13), 144.2 (C7), 141.5
(C8), 139.9 (C17), 138.9 (C15), 131.0 (C6), 130.9 (C5),
129.9, 128.1, 127.5, 127.4, 125.8, 124.9 (C2, C3, C4,
C14, C16, C18), 120.9 (C10), 115.1 (C9), 55.4 (C12),
34.6 (C(O)Me). IR (KBr): 1693 cm−1, w(CO). Mass
found: m/z=721.1408. [C40H31N4O3Pd]+ calc.: m/z=
721.1431. No correct microanalysis was obtained due
to the presence of a small amount (5–10%) of
[Pd(C(O)Me)(phen)2]SO3CF3.
1
4a: H-NMR (CDCl3): l 8.04 (d, J=8.4 Hz, H5),
7.6–7.2 (22H, m, PhꢀP, H4), 6.99 (d, J=7.2 Hz,
H3), 6.89 (d, J=8.7 Hz, H10), 6.67 (d, J=8.7 Hz,
H9), 3.95 (s, H12), 2.6–2.1 (4H, m, CH2P), 0.57 (dd,
J=6.3, 2.8 Hz, MeꢀPd). 31P-NMR (CDCl3): l 59.1
(d, J=27 Hz, P cis to Me), 39.1 (d, J=27 Hz, P
trans to Me). Mass found: m/z=911.2171.
[C53H47N2O2P2Pd]+ calc.: m/z=911.2148.
2.4. Synthesis of [Pd(C(O)Me)(p-An-BIAN)(LꢀL)]SO3-
CF3 (LꢀL=dmphen (3b), dppe (4b))
A solution of [Pd(Me)(p-An-BIAN)(dmphen)]SO3-
CF3 (3a) (30.2 mg, 0.035 mmol) in dichloromethane
(20 ml) was placed in a 100 ml stainless-steel auto-
clave, and CO was introduced up to 15
1
5a: H-NMR (CDCl3): l 8.00 (d, J=8.3 Hz, H5),
7.43 (pst, H4), 7.3–6.9 (30H, m, PhꢀP, H3, H9, H10),