Notes
Organometallics, Vol. 19, No. 19, 2000 3993
least-squares techniques against F2 (SHELXL-93).13 XP (Sie-
mens Analytical X-ray Instruments, Inc.) was used for struc-
ture representations.
P h C(O)CHdP P h 2CH2CH2P P h 2dCHC(O)P h (1). Mp: 236
°C. Anal. Calcd for C42H36O2P2‚1/3CH2Cl2 (634.69): C, 76.69;
1
H, 5.57. Found: C, 76.84; H, 5.62. H NMR (CD2Cl2; δ, ppm):
3.24 (“d”, 4H, P-CH2), 4.24 (“t”, 2H, PdCH), 7.40 (m, 6H,
C-Ph), 7.46 (8H, P-Ph m), 7.54 (4H, P-Ph p), 7.78 (8H, P-Ph
o), 7.98 (m, 4H, C-Ph). 13C NMR (CD2Cl2; δ, ppm): 18.9 (“t”,
P-CH2), 47.1 (“t”, PdCH), 127.1 (Ph), 127.9 (i-C(O)Ph), 128.1
(Ph), 129.5 (“t”, o/m-P-Ph), 129.7 (p-C-Ph), 132.0 (“t”, o/m-
P-Ph), 132.5 (Ph), 141.5 (“t”, i-P-Ph), 185.5 (CO). 31P NMR
(CD2Cl2; δ, ppm): 17.7. IR (KBr; v˜CO, cm-1): 1509.
[P h C(O)CHdP P h 2CH2CH2P P h 2dCHC(O)P h ]P d Cl2 (2).
Cl2Pd(PhCN)2 (225 mg, 0.59 mmol) in 20 mL of CH2Cl2 was
added to PhC(O)CHdPPh2CH2CH2PPh2dCHC(O)Ph (373 mg,
0.59 mmol) in 20 mL of CH2Cl2. After it was stirred for 1 h,
the solution was filtered, concentrated in vacuo, and layered
with n-hexane. At -30 °C a yellow solid (220 mg, 46%)
precipitated.
Mp: 225 °C dec. Anal. Calcd for C42H36Cl2O2P2Pd‚CH2Cl2
(812.02): C, 57.58; H, 4.27. Found: C, 57.77; H, 4.51. 1H NMR
(CD2Cl2; δ, ppm): 2.90 (m, 2H, CH2), 3.11 (m, 1H, CH2), 3.44
(m, 1H, CH2), 4.42 (d, 2J H,P ) 2.9 Hz, 1-H), 5.95 (d, 2J H,P ) 1.1
Hz, 9-H), 7.91/6.66/7.14 (o/m/p, 1-benzoyl), 8.54/7.52/7.63 (o/
m/p, 9-benzoyl), 7.50/7.65/8.29/8.48 (2H each, o-P-Ph). 13C
NMR (CD2Cl2; δ, ppm (J C,P)): 16.7 (62 Hz, CH2), 20.1 (63 Hz,
F igu r e 1. Crystal structure of 2. The thermal ellipsoids
correspond to 30% probability. Selected bond lengths (Å)
and angles (deg): C1-P1 ) 1.816(6), C9-P2 ) 1.787(6),
Pd-Cl1 ) 2.380(2), Pd-Cl2 ) 2.337(2); Cl1-Pd-Cl2 )
88.82(6), C1-Pd-C9 ) 94.9(2).
1
1
CH2), 21.0 (48 Hz, J C,H ) 143 Hz, C9), 27.6 (43 Hz, J C,H
)
133 Hz, C1), 129.1/127.7/131.8 (o/m/p, 1-benzoyl), 129.9, 133.5,
133.4 (o/m/p, 9-benzoyl), 131.9 (9 Hz)/133.0 (9 Hz)/134.5 (10
Hz)/136.6 (10 Hz) (o-P-Ph), 128.5 (13 Hz)/129.8 (12 Hz)/129.9
(12 Hz)/130.1 (12 Hz) (m-P-Ph), 200.1/202.1 (CO). 31P NMR
2
2
(CD2Cl2; δ, ppm): 29.8 (d, J P,P ) 4 Hz, P1), 33.1 (d, J P,P ) 4
Hz, P2). IR (KBr; v˜CO, cm-1): 1679, 1632.
[P h 3P dCHC(NMe2)dCH2]P d Cl2 (3). Cl2Pd(PhCN)2 (302
mg, 0.79 mmol) in 20 mL of CH2Cl2 was added to Ph3PdCHC-
(NMe2)dCH2 (272 mg, 0.79 mmol) in 20 mL of CH2Cl2. The
reaction mixture was stirred for 1 h and then filtered. The
filtrate was concentrated in vacuo and layered with n-hexane.
At -30 °C a yellow solid (144 mg, 35%) precipitated. Mp: 214
°C. Anal. Calcd for C23H24Cl2NPPd (522.75): C, 52.85; H, 4.63;
1
N, 2.68. Found: C, 52.46; H, 4.36; N, 2.51. H NMR (CD2Cl2;
δ, ppm): 1.54 (d, 2J H,H ) 5.5 Hz, CH2(E)), 2.98 (s, NMe2), 3.08
F igu r e 2. Crystal structure of 3. Hydrogen atoms are
omitted for clarity. The thermal ellipsoids correspond to
30% probability. Selected bond lengths (Å) and angles
(deg): Pd-Cl1 ) 2.359(3), Pd-Cl2 ) 2.389(3), Pd-C1 )
2.108(12), Pd-C2 ) 2.231(12), Pd-C3 ) 2.090(12), C1-P
) 1.77(1), C1-C2 ) 1.46(2), C2-C3 ) 1.44(2); Cl1-Pd-
Cl2 ) 97.0(1).
2
4
4
(dd, J H,H ) 5.5 Hz, J H,H ) 2.9 Hz, CH2(Z)), 3.98 (dd, J H,H
)
2
2.9 Hz, J H,P ) 3.6 Hz), 7.67 (m, m-CH), 7.80 (m, p-CH), 7.87
(m, o-CH). 13C NMR (CD2Cl2; δ, ppm): 28.0 (1J C,P ) 76 Hz,
1J C,H ) 151 Hz, CH), 38.3 (1J C,H ) 161 Hz, CH2), 40.3 (1J C,H
)
138 Hz, NMe2), 121.8 (1J C,P ) 89 Hz, i-C), 130.1 (3J C,P ) 13
Hz, m-CH), 134.5 (2J C,P ) 10 Hz, o-CH), 134.9 (4J C,P ) 3 Hz,
p-CH), 144.7 (2J C,P ) 7 Hz, Cquat). 31P NMR (CD2Cl2; δ, ppm):
18.6. IR (Nujol; v˜CCC, cm-1): 1541.
Magna 550 spectrometer. X-ray data of compound 2 and 311
were collected on a STOE-IPDS diffractometer using graphite-
monochromated Mo KR radiation. The structures were solved
by direct methods (SHELXS-86)12 and refined by full-matrix
Ack n ow led gm en t. We gratefully acknowledge the
financial support from the Max-Planck-Gesellschaft and
the Fonds der Chemischen Industrie.
(11) For the X-ray crystal structure analysis suitable crystals of 2
and 3 were obtained from a CH2Cl2/hexane solution. The crystals of
both complexes contain CH2Cl2 as solvent. Crystal data for 2: crystal
dimensions 0.4 × 0.3 × 0.3 mm, yellow prisms, space group P21/n,
monoclinic, a ) 11.832(2) Å, b ) 16.017(3) Å, c ) 25.262(5) Å, â )
96.11(3)°, V ) 4760(2) Å3, Z ) 4, Fcalcd ) 1.488 g cm-3, 12 728 reflections
measured, 7000 were independent of symmetry and 4594 were
observed (I > 2σ(I)), R1 ) 0.056, wR2(all data) ) 0.149, 505 param-
eters. Crystal data for 3: crystal dimensions 0.2 × 0.1 × 0.1, yellow
prisms, space group P1h, triclinic, a ) 8.395(2) Å, b ) 12.482(2) Å, c )
13.202(3) Å, R ) 99.94(3)°, â ) 91.40(3)°, γ ) 94.95(3)°, V ) 1356.5(5)
Å3, Z ) 2, Fcalcd ) 1.592 g cm-3, 2782 reflections measured, 2782 were
independent of symmetry, and 1777 were observed (I > 2σ(I)), R1 )
0.070, wR2(all data) ) 0.182, 281 parameters.
Su p p or tin g In for m a tion Ava ila ble: Tables of crystal
data and structure refinement details, atomic coordinates,
bond lengths and angles, anisotropic displacement parameters,
and hydrogen coordinates for 2 and 3. This material is
OM000429Z
(13) Sheldrick, G. M. SHELXL-93; University of Go¨ttingen, Go¨ttin-
gen, Germany, 1993.
(12) Sheldrick, G. M. Acta Crystallogr. 1990, A46, 467.