New orthopalladated complexes of phosphorus ylides

Article abstract of DOI:10.1016/j.poly.2008.07.017

This work reports on the preparation of the complexes [PdCl₂(Y¹)₂], [PdCl₂(Y²)₂] (Y¹ = (p-tolyl)₃PCHCOCH₃ (1a); Y² = Ph₃PCHCO₂

Full text of DOI:10.1016/j.poly.2008.07.017

Polyhedron 27 (2008) 3275–3279
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
New orthopalladated complexes of phosphorus ylides: Crystal structure
of [Pd{CH{P(C7H6)(p-tolyl)2}COCH3}Cl{P(p-tolyl)3}]
a
a
b
Seyyed Javad Sabounchei a, , Hassan Nemattalab , Fateme Akhlaghi , Hamid Reza Khavasi
*
a Faculty of Chemistry, Bu-Ali Sina University, Hamedan 65174, Iran
b Department of Chemistry, Shahid Beheshti University, Evin, Tehran 1983963113, Iran
a r t i c l e i n f o
a b s t r a c t
This work reports on the preparation of the complexes [PdCl2(Y1)2], [PdCl2(Y2)2] (Y1 = (p-tolyl)3PCHCOCH3
(1a); Y2 = Ph3PCHCO2CH2Ph (1b)), [Pd{CHP(C7H6)(p-tolyl)2COCH3}(
-Cl)]2 (2a), [Pd{CHP(C6H4)Ph2CO2-
CH2Ph}( -Cl)]2 (2b), [Pd{CH{P(C7H6)(p-tolyl)2}COCH3}Cl(L)] (L = PPh3 (3a), P(p-tolyl)3 (4a)) and
[Pd{CH{P(C6H4)Ph2}CO2CH2Ph}Cl(L)] (L = PPh3 (3b), P(p-tolyl)3 (4b)). Orthometallation and ylide C-coor-
dination in complexes 2a–4b are demonstrated by an X-ray diffraction study of 4a.
Ó 2008 Elsevier Ltd. All rights reserved.
Article history:
Received 11 June 2008
Accepted 9 July 2008
Available online 1 September 2008
l
l
Keywords:
Orthopalladation
Orthometallation
Triphenylphosphine
Triparatolylphosphine
Phosphorus ylide
1. Introduction
2. Experimental
The activation of C–H bonds induced by transition metals is, at
present, one of the most active fields of research in organometallic
chemistry due to its implications, among others, in the fundamen-
tal steps in catalytic cycles, in the functionalization of simple sub-
strates through orthometallation, and in other relevant chemical
processes [1–14]. The orthometallation of the phosphorus ylides
R3PC = (R0)R00 (R, R0 and R00 = alkyl or aryl groups) [15–19] is pro-
duced, in the vast majority of cases, regioselectively at the Ph rings
of the phosphine unit. In 1989, Vicente et al. [20] presented a
method for the synthesis of orthopalladated adducts of the phos-
phorus ylide Ph3P@CHCO2Me. Some recent contributions have
shown, however, that it is possible to obtain orthopalladated com-
plexes derived from CH activation at Ph rings belonging to the R0 or
R00 substituents of the ylidic carbon atom and, more precisely,
belonging to benzamide moieties [21]. Although orthometallation
of ylides is well-known [17,20,22–26], in this work we describe
the synthesis and characterization of Pd(II) complexes of the titled
phosphorus ylides. The X-ray crystal structure of complex 4a ade-
quately shows the orthopalladation and ylide C-coordination in
complexes 2a–4b.
2.1. Physical measurements and materials
Melting points were measured on a SMPI apparatus. Elemental
analyses for C and H were performed using a PE 2400 series II ana-
lyzer. IR spectra were recorded on a Shimadzu FT IR 435-U-04
spectrophotometer (KBr pellets). NMR spectra were obtained on
a 300 MHz Bruker FT-NMR spectrometer in DMSO-d6 or CDCl3 as
the solvent. Chemical shifts (d) are reported relative to internal
TMS and external 85% phosphoric acid. The single crystal X-ray dif-
fraction analysis for complex 4a was performed on a STOE IPDS-II
two circle diffractometer at 120(2) K, using graphite monochro-
mated Mo K
was performed at 120(2) K using the
a
X-ray radiation (k = 0.71073 Å). The data collection
-scan technique and using
x
the STOE X-AREA software package [27]. The crystal structure was
solved by direct methods [28] and refined using the X-STEP32 crys-
tallographic software package [29]. All of the non-hydrogen atoms
were refined anisotropically. All of the hydrogen atoms were lo-
cated in ideal positions. Methanol was dried using magnesium
powder just before use. All other solvents were reagent grade
and were used without further purification.
2.2. Sample preparation
The ligands [(p-tolyl)3PCHCOCH3] (Y1) and [Ph3PCHCO2CH2Ph]
* Corresponding author.
E-mail address: jsabounchei@yahoo.co.uk (S.J. Sabounchei).
(Y2) were prepared based on the published methods [30,31].
0277-5387/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2008.07.017

3276
S.J. Sabounchei et al. / Polyhedron 27 (2008) 3275–3279
3
1
2.2.1. Synthesis of [PdCl2(Y1)2] (1a) general procedure
3CH3), 31.45 (d, JPC = 11.30 Hz, COCH3), 50.09 (d, JPC = 63.64 Hz,
To a saturated solution of PdCl2 (0.049 g, 0.28 mmol) in acetoni-
trile (10 ml) was added solid Y1 (0.198 g, 0.55 mmol), and the sus-
pension was stirred for 15 min. The resulting brown solution was
concentrated (2 ml) and diethyl ether (10 ml) was added to precip-
itate the brown solid 1a. Anal. Calc. for C48H50Cl2O2P2Pd: C, 64.19;
H, 5.61. Found: C, 64.0; H, 5.79%. Yield 0.185 g (75%), m.p. 170–
CH), 124.02–142.96 (m, arom.), 201.68 (CO).
2.2.6. Data for [Pd{CH{P(C7H6)(p-tolyl)2}COCH3}Cl(PPh3)] (3b)
White solid. Anal. Calc. for C45H37ClO2P2Pd: C, 66.43; H, 4.58.
Found: C, 66.09; H, 4.93%. Yield 0.079 g (81%), m.p. 222–224 °C.
IR (KBr disk)
m
(cmꢀ1): 1677 (C@O), 1434, 1303, 1132, 1109, 855
172 °C. IR (KBr disk)
m
(cmꢀ1): 1643 (C@O), 1599, 1498, 1399,
(P–C), 751, 690. 1H NMR (CDCl3) dH (ppm): 4.19 (dd, 2JPH = 9.02 Hz,
3JPH = 5.82 Hz, 1H, CH), 5.15 (s, CH2), 6.9–7.8 (m, arom.). 31P NMR
(CDCl3) dP (ppm): 13.70 (PPh3) and 27.86 (P(p-tolyl)2) (2d,
3JPP = 19.21 Hz). 13C NMR (CDCl3) dC (ppm): 35.55 (dd,
1347, 1293, 1191, 1147, 1104, 1020, 966, 873, 806 (P–C), 763,
658. 1H NMR (CDCl3) dH (ppm): 2.25 (3H, s, COCH3), 2.39 (9H, s,
3CH3), 5.09 (br, CH), 7.26–7.66 (12H, m, arom.). 31P NMR (CDCl3)
dP (ppm): 23.52 and 23.38 (2s, at 25 °C), 23.50 (1s, at 55 °C). 13C
1JPC = 70.69 Hz, JPC = 61.25 Hz, CH), 65.31 (s, CH2), 122.82–139.81
2
3
NMR (CDCl3) dC (ppm): 22.13 (s, 3CH3), 32.63 (d, JPC = 16.38 Hz,
(m, arom.), 172.16 (s, CO).
1
COCH3), 119.28 (d, JPC = 149.8 Hz, p-tolyl, (ipso)), 135.04 (d,
3
2JPC = 7.35 Hz, p-tolyl, (ortho)), 130.15 (d, JPC = 21.64 Hz, p-tolyl,
2.2.7. Synthesis of [Pd{CH{P(C7H6)(p-tolyl)2}COCH3}Cl{P(p-tolyl)3}]
(4a) general procedure
4
(meta)), 135.12 (d, JPC = 7.35 Hz, p-tolyl, (para)), 205.16 (CO).
To a suspension of complex 2a (0.046 g, 0.06 mmol) in CH2Cl2
(20 ml) was added solid P(p-tolyl)3 (0.039 g, 0.13 mmol). The mix-
ture was stirred for 30 min. The resulting colorless solution was
concentrated (2 ml) and diethyl ether (30 ml) was added to precip-
itate the white solid 4a. Anal. Calc. for C45H45ClOP2Pd: C, 67.09; H,
5.63. Found: C, 67.22; H, 5.89%. Yield 0.071 g (84%), m.p. 252–
2.2.2. Data for [PdCl2(Y2)2] (1b)
Orange solid. Anal. Calc. for C54H46Cl2O4P2Pd: C, 64.11; H, 4.89.
Found: C, 64.97; H, 4.64%. Yield 0.217 g (78%), m.p. 184–186 °C. IR
(KBr disk)
m
(cmꢀ1): 1683 (C@O), 1435, 1285, 1128, 1106, 836 (P–
C), 801, 741, 688. 1H NMR (DMSO-d6) dH (ppm): 4.95 (s, CH2, minor
diastereoisomer) 5.10 (s, CH2, major diastereoisomer) 5.36 (bd,
2JPH = 14.33 HZ, CH, two diastereoisomers), 7.22–7.81 (20H, m,
arom.). 31P NMR (DMSO-d6) dP (ppm): 19.83 (trans, minor diaste-
reoisomer), 20.80 (trans, major diastereoisomer), 27.84 (cis, minor
diastereoisomer), 28.09 (cis, major diastereoisomer). 13C NMR
(DMSO-d6) dC (ppm): 28.61 (d, 1JPC = 52.24 Hz, CH, minor diastereo-
254 °C. IR (KBr disk)
m
(cmꢀ1): 1641 (C@O), 1598, 1497, 1444,
1396, 1295, 1189, 1152, 1104, 1027, 802 (P–C), 649, 511 1H NMR
(CDCl3) dH (ppm): 1.67 (3H, s, COCH3), 2.31 and 2.43 (9H, 2s,
2
3
3CH3), 4.88 (dd, JPH = 9.85 Hz, JPH = 9.22 Hz, 1H, CH), 7.03–7.62
(23H, m, arom.). 31P NMR (CDCl3) dP (ppm): 11.56 (P(p-tolyl)3)
and 26.97 (P(p-tolyl)2) (2d, JPP = 18.5 Hz). 13C NMR (CDCl3) dC
3
1
3
isomer), 29.38 (d, JPC = 56.75 Hz, CH, major diastereoisomer),
(ppm): 21.43 (s, 3CH3), 31.24 (d, JPC = 11.06 Hz, COCH3), 49.90
(d, JPC = 60.71 Hz, CH), 122.02–165.18 (m, arom.), 201.31 (CO).
1
64.94 (s, CH2, minor diastereoisomer), 67.62 (s, CH2, major diaste-
reoisomer), 115.79–136.05 (arom.), 164.19 (CO, minor diastereo-
isomer), 170.45 (CO, major diastereoisomer).
2.2.8. Data for [Pd{CH{P(C6H4)Ph2}CO2CH2Ph}Cl{P(p-tolyl)3}] (4b)
White solid. Anal. Calc. for C48H46ClO2P2Pd: C, 67.14; H, 5.40.
Found: C, 66.27; H, 5.31%. Yield 0.087 g (85%); m.p. 234–236 °C.
2.2.3. Synthesis of [Pd{CH{P(C7H6)(p-tolyl)2}COCH3}(
general procedure
l-Cl)]2 (2a)
IR (KBr disk):
m
(cmꢀ1): 1688 (C@O), 1436, 1294, 1128, 844 (P–
To a suspension of PdCl2 (0.090 g, 0.51 mmol) in acetonitrile
(20 ml) was added solid Y1 (0.376 g, 1.02 mmol). The mixture
was refluxed for 8 h and then allowed to cool to room temperature.
The suspension was filtered and the solid was washed with diethyl
ether (10 ml) to give a greenish-yellow solid as product 2a. The
phosphonium salt [(p-tolyl)3PCH2COCH3]Cl separated, as a by-
product, via the mother liquor by washing solid 2a. Anal. Calc. for
C), 806, 734, 692. 1H NMR (CDCl3) dH (ppm): 4.18 (dd,
2JPH = 9.05 Hz, JPH = 5.31 Hz, 1H, CH), 5.156 (s, 2H, CH2), 2.30 (s,
3
9H, 3CH3), 6.9–8 (m, 31H, arom). 31P NMR (CDCl3) dP (ppm):
13.51 (P(p-tolyl)3), 26.47 (PPh2), (2d, JPP = 18.5 Hz). 13C NMR
3
1
2
(CDCl3) dC (ppm): 35.27 (dd, JPC = 69.3 Hz, JPC = 61.02 Hz, CH),
65.12 (s, CH2), 122.62–139.44 (m, arom.), 172.06 (s, CO).
C
48H48Cl2O2P2Pd2: C, 57.50; H, 4.83. Found: C, 57.0; H, 5.06%. Yield
0.356 g (78%), m.p. 316–319 °C. IR (KBr disk)
(cmꢀ1): 1645, 1599,
1441, 1292, 1193, 1152, 1108, 1030, 805 (P–C), 656.
3. Results and discussion
m
3.1. Spectroscopy
2.2.4. Data for [Pd{CHP(C6H4)Ph2CO2CH2Ph}(
l
-Cl)]2 (2b)
The m(CO) band, which is sensitive to complexation, occurs at
Greenish-yellow solid. Anal. Calc. for C54H44Cl2O4P2Pd2: C,
1600 and 1610 cmꢀ1 in the parent ylides Y1 and Y2, respectively
[30,31]. Coordination of ylide through the carbon atom causes an
58.82; H, 4.02. Found: C, 58.76; H, 4.40%. Yield 0.210 g (75%),
m.p. 283–285 °C. IR (KBr disk)
m
(cmꢀ1): 1695 (C@O), 1435, 1284,
increase in the
of the (CO) band is expected [32]. Thus the IR absorption bands for
the complexes at higher frequencies indicate that C-coordination
m(CO) band, whereas for O-coordination a lowering
1126, 1106, 836 (P–C), 734, 689.
m
2.2.5. Synthesis of [Pd{CH{P(C7H6)(p-tolyl)2}COCH3}Cl(PPh3)] (3a)
general procedure
has occurred. The m(P–C) band frequencies, which are also diagnos-
tic of the coordination mode, occur at 848 and 887 cmꢀ1 in the par-
ent ylides Y1 and Y2, respectively, and are shifted to lower
frequencies for the complexes, suggesting some removal of the
electron density of the P–C bonds [33].
To a suspension of complex 2a (0.046 g, 0.06 mmol) in CH2Cl2
(20 ml) was added solid PPh3 (0.033 g, 0.13 mmol). The mixture
was stirred for 30 min. The resulting colorless solution was con-
centrated (2 ml) and diethyl ether (30 ml) was added to precipitate
the white solid 3a. Anal. Calc. for C42H39ClOP2Pd: C, 66.06; H, 5.15.
Found: C, 65.89; H, 5.35%. Yield 0.064 g (82%), m.p. 246–248 °C. IR
The presence of two chiral C centres (forming diastereoisomers)
in 1b (Scheme 1) is shown in the 1H, 31P and 13C NMR spectra by
two sets of signals with unequal populations for CH2, CH, CO and
PCH groups. The geometry of cis and trans may leads to the further
peaks in the 31P NMR spectra: 19.83, 20.80, 27.84 and 28.09 ppm
for 1b and 23.38 and 23.52 ppm at 25 °C for 1a [34,35].
The two geometries for 1a equilibrate rapidly at higher temper-
atures, leading to one signal for phosphorus centre (dP = 23.50 ppm
at 55 °C) (Fig. 1).
(KBr disk)
m
(cmꢀ1): 1639, 1594, 1572, 1475, 1433, 1351, 1302,
1180, 1154, 1103, 803 (P–C), 747, 692, 556. 1H NMR (CDCl3) dH
(ppm): 1.66 (3H, s, COCH3), 2.37 and 2.42 (9H, 2s, 3CH3), 4.90
2
3
(dd, JPH = 8.96 Hz, JPH = 8.87 Hz, 1H, CH), 6.66–7.78 (26H, m,
arom.). 31P NMR (CDCl3) dP (ppm): 12.00 (PPh3) and 28.49 (P(p-to-
lyl)2) (2d, JPP = 19.0 Hz). 13C NMR (CDCl3) dC (ppm): 21.65 (s,
3

S.J. Sabounchei et al. / Polyhedron 27 (2008) 3275–3279
3277
CH3CN, n = 2
PdCl2 + nAr3PCHCOR1
PdCl2[Ar3 PCHCOR1]2
r t, 15 min
R2
(1a and 1b)
CH3CN
reflux
n = 1
COR1
COR1
Cl
L
CH
Pd
CH
Ar2P Pd
Cl
+2L
Pd
PAr2
2
Ar2P
r t 30 min
Cl
CH
R1
R2
R2
(3a, 3b, 4a and 4b)
(2a and 2b)
No 1a
2a
3a
4a
1b
2b
3b
4b
Ar P(p-tolyl)3
P(p-tolyl)3
P(p-tolyl)3
Me
P(p-tolyl)3
Me
Ph
Ph
Ph
Ph
R1 Me
Me
Me
-
OCH2Ph
OCH2Ph
OCH2Ph
H
OCH2Ph
H
R2
L
-
-
Me
Me
-
-
H
-
PPh3
P(p-tolyl)3
PPh3
P(p-tolyl)3
Scheme 1.
Table 1
Crystal data and structure refinement for 4a
Compound
4a
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
Space group
a (Å)
C
45H45ClOP2Pd
805.62
120(2)
0.71073
triclinic
P1
9.973(2)
ꢀ
b (Å)
c (Å)
13.211(3)
16.830(4)
73.082(19)
89.549(19)
68.566(18)
1962.6(8)
2
1.363
0.656
832
a
(°)
b (°)
c
(°)
Volume (Å3)
Z
DCalc (Mg/m3)
Absorption coefficient (mmꢀ1
F(000)
)
Crystal size (mm)
0.50 ꢁ 0.20 ꢁ 0.10
1.74–29.51
20212/10443 (0.0902)
ꢀ12 6 h 6 13,
ꢀ18 6 k 6 18,
ꢀ23 6 l 6 21
96.7
h Range for data collection (°)
Reflections collected/unique (Rint
Limiting indices
)
Completeness to h = 29.51° (%)
Absorption correction
Maximum and minimum transmission
Refinement method
numerical
0.930 and 0.850
full-matrix least-squares on F2
10443/0/450
Fig. 1. Variable temperature 31P NMR study on 1a.
Data/restraints/parameters
Goodness-of-fit on F2
1.088
Final R indices [I > 2
R indices (all data)
Extinction coefficient
Largest difference in peak and hole (e Åꢀ3
r
(I)]
R1 = 0.0905, wR2 = 0.1877
R1 = 0.0999, wR2 = 0.1959
0.019(3)
1.723 and ꢀ1.918
In the 1H NMR spectra for 1a and 1b, the signals due to the
methinic proton are broad (1a) or are a broad doublet (1b). This
broadening is probably due to the presence of different geometries
and the above mentioned diastereoisomers. A related insoluble
complex, [PdCl2{CH(PPh3)CO2Me}2], has been reported to be of a
trans geometry on the basis of IR data [20]. An NMR study could
not be performed on complexes 2a and 2b because they are very
insoluble in the most common solvents. However their elemental
analysis, IR spectra and the synthesis of 3a and 4b from complexes
2a and 2b adequately establish their identity, thus we propose for
2a and 2b the same structure as reported for the related complexes
[17,20,22–26] (see Scheme 1). The bridge-splitting reaction of 2a
)
and 2b with PPh3 and P(p-tolyl)3 is highly selective, affording
exclusively the corresponding mononuclear compounds 3a, 4a,
3b and 4b, respectively (Scheme 1). The 1H and 31P signals for
the PCH group of complexes 3a–4b are shifted downfield com-
pared to that of the free ylide, as a consequence of the inductive ef-
fect of the metal centre. The 1H NMR spectra of complexes 3a–4b
show one doublet of doublets signal for the CH group that must

3278
S.J. Sabounchei et al. / Polyhedron 27 (2008) 3275–3279
Fig. 2. ORTEP view of the X-ray crystal structure of [Pd{CH{P(C7H6)(p-tolyl)2}COCH3}Cl{P(p-tolyl)3}] (4a). Selected bond lengths (Å) and bond angles (°): Pd(1)–C(12),
2.021(5); Pd(1)–C(3), 2.166(5); Pd(1)–P(2), 2.2945(15); Pd(1)–Cl(1), 2.4241(14); C(2)–C(3), 1.478(8); C(2)–O(1), 1.219(8); C(11)–C(12), 1.415(7); C(11)–P(1), 1.782(6); C(3)–
P(1), 1.780(5); C(12)–Pd(1)–C(3), 86.8(2); C(12)–Pd(1)–P(2), 93.06(14); C(3)–Pd(1)–P(2), 168.19(16); C(12)–Pd(1)–Cl(1), 170.58(14); C(3)–Pd(1)–Cl(1), 88.35(15); P(2)–
Pd(1)–Cl(1), 93.33(5) (hydrogen atoms have been omitted for clarity).
arise from the simultaneously coupling with two phosphorus
centres.
[41] and ½Pdf
j
2-C;O—C6H4fCðOÞMeg-2gBrfPðo-ToÞ3gꢃ (2.021(2) Å)
[42]. The distances Pd(1)–C(12) [2.021(5) Å] and Pd(1)–C(3)
[2.166(5) Å] are different, probably reflecting the different trans ef-
fect of the phosphorus and chlorine atoms. The stabilized reso-
nance structure for the parent ylide is destroyed by the complex
formation, thus the C(2)–C(3) bond length (1.478(8) Å) is signifi-
cantly longer than the corresponding distance found in the similar
uncomplexed phosphoranes (1.407(8) Å [43] and 1.401(2) Å [44]).
In 13C NMR spectra, a higher shielding of the ylidic carbon atoms
compared to those of the parent ylides is expected and we observed
this for 3a, 4a and 1b. Such a higher shielding was observed in
Â
Ã
PdClð
g
3-2-XC3H4ÞðC6H5Þ3PCHCOR (X = H, CH3; R = CH3, C6H5),
and is due to the change in hybridization of the ylidic carbon atom
on coordination [36]. Similar upfield shifts of 2–3 ppm with refer-
ence to the parent ylide were also observed in the case of
[(C6H5)3PC5H4 ꢂ HgI2]2 [37] and in our synthesized complexes
[30,38]. The downfield shift of the carbonyl C atom in 1a, 3a, 3b, 4a
and 4b compared to the same carbon atom in the parent ylides
(190.38 ppm (Y1) and 170.46 ppm (Y2)), indicate a much lower
shielding of the CO group in these complexes [30,38–40]. In this
work, it is interesting that the expected upfield shift of the ylidic C
atoms in 3b and 4b and downfield shift of the carbonyl C atom in
1b are not in accordance with the expected process. This is probably
due to the steric nature of Y2, which is different from ketonic ylides.
Likewise the C(3)–P(1) bond length in
1.7194(17) Å [44], which shows that the corresponding bond in
4a is considerably elongated to 1.780(5) Å.
a similar ylide is
4. Conclusion
The present study describes the synthesis and characterization
of orthometallated Pd(II) complexes of phosphorus ylides. On the
basis of the physico-chemical and spectroscopic data we propose
that these ligands herein exhibit C-coordination to the metal cen-
tre, which is further confirmed by the X-ray crystal structure of
complex 4a. The structural study involved in this work demon-
strates that phosphorus ylides can show transition metal induced
activation of C–H bonds.
3.2. X-ray crystallography
Table 1 provides the crystallographic results and refinement
information for complex 4a. The molecular structure and pertinent
bond distances and angles are presented in Fig. 2.
Acknowledgement
Suitable crystals of 4a were grown by the slow diffusion of
diethyl ether into a chloroform solution. The Pd atom is located
in a distorted square-planar environment, surrounded by one
ylidic carbon (C3) and one metallated carbon (C12) that form a
five-membered cycle, one chlorine (Cl1) and one phosphorus (P2)
atom. The angles subtended by the ligands at the Pd(II) centre
in 4a vary from 86.8(2)° to 93.33(5)° and 168.19(16)° to
170.58(14)° indicating the distorted square-planar environment.
The C(3)–Pd(1)–P(2) (168.19(16)°) and C(12)–Pd(1)–Cl(1) (170.58-
(14)°) bond angles deviate a little from linearity. The Pd(1)–C(12)
bond distance (2.021(5) Å) is statistically identical to those found
We are highly grateful to Mr. Zebarjadian for recording the NMR
spectra.
Appendix A. Supplementary data
CCDC 684309 contains the supplementary crystallographic data
for 4a. These data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
UK; fax: (+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.poly.2008.07.017.
in the orthopalladated complexes ½Pdf
j
2-C; N—C6H4-1-½ð3; 5-
Me2—C3N2Þ—CH2—ð
g
5-C5H4Feð
g
5-C5H5ÞꢃgClðPPh3Þꢃ
(2.035(5) Å)

S.J. Sabounchei et al. / Polyhedron 27 (2008) 3275–3279
3279
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Urriolabeitia, J. Organomet. Chem. 693 (2008) 417.
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