Substitution reactions of trans-[PdXPh(SbPh3)2J (X=Cl or Br) with nitrogen, phosphines and arsenic donor ligands. Crystal structures of trans-[PdClPh(PPh3)2], [PdClPh(bipy)], [PdClPh(dppm)]2, and [PdB

Article abstract of DOI:10.1016/S0277-5387(98)00404-5

Exchange reactions of trans-[PdXPh(SbPh₃)₂] (1) (X=Cl or Br) with ligands L in refluxing dichloromethane give the palladium phenyl complexes [PdXPhL₂] (X=Cl, L=PPh₃, AsPh₃, L₂=2,2′-bipyridi

Full text of DOI:10.1016/S0277-5387(98)00404-5

Polyhedron 18 (1999) 1141–1145
Substitution reactions of trans-[PdXPh(SbPh3)2J (X5Cl or Br) with
nitrogen, phosphines and arsenic donor ligands. Crystal structures of trans-
[PdClPh(PPh3)2], [PdClPh(bipy)], [PdClPh(dppm)]2, and [PdBrPh(dppm)]2
b
b
Ayfer Mentesa, Raymond D.W. Kemmitta, , John Fawcett , David R. Russeli
*
aInorganic Research Laboratories, Department of Chemistry, The University of Leicester, Leicester, LE1 7RH, UK
bX-Ray Crystallography Laboratory, Department of Chemistry, The University of Leicester, Leicester, LE1 7RH, UK
Received 24 September 1998; accepted 3 November 1998
Abstract
Exchange reactions of trans-[PdXPh(SbPh3)2] (1) (X5Cl or Br) with ligands L in refluxing dichloromethane give the palladium
phenyl complexes [PdXPhL2] (X5Cl, L5PPh3, AsPh3, L252,29-bipyridine (bipy), 4,49-dimethyl-2,29-bipyridine (dmbipy), 1,10-
phenanthroline (phen); X5Br, L5PPh3, L25bipy). Treatment of the complexes with bis(diphenylphosphino)methane (dppm) in refluxing
1
dichloromethane gives [PdXPh(dppm]2. These complexes have been characterised by microanalysis, IR and H NMR spectroscopic data
together with single crystal X-ray determinations of the phenyl palladium complexes, trans-[PdClPh(PPh3)2], [PdClPh(bipy)],
[PdClPh(dppm)]2, and [PdBrPh(dppm)]2.
1999 Elsevier Science Ltd. All rights reserved.
Keywords: Palladium; Bipyridyl; Diphenylphosphinomethane; Crystal structure
We have previously reported the synthesis and charac-
terisation of the complexes trans-[PdClPh(SbPh3)2] (1a),
and [PdBrPh(SbPh3)2] (1b), [1]. We now report that the
triphenylantimony ligands in these complexes can be
readily displaced by nitrogen, phosphorus and arsenic
donor ligands to afford a convenient synthesis of a variety
of palladium phenyl complexes including the new dinu-
afforded the phenyl-palladium complexes (2), Scheme 1.
The dimeric bis(diphenylphosphino)methane bridged com-
plexes of palladium are also conveniently prepared using
this method, Scheme 2.
The molecular structure of the complex (2a) is shown in
Fig. 1 which also gives the crystallographic numbering
scheme. Selected bond distances and angles are given in
Table 1. The geometry at the palladium in (2a) is square
planar with trans phosphine donors and phenyl trans to
clear
bis(diphenylphosphino)methane
complexes
[PdXPh(dppm)]2, (X5Cl or Br). Some nitrogen donor
ligand complexes of the type [PdXPh(bipy)], (X5Cl, 2d;
X5Br, 2e, X5I), has been previously synthesised using
˚
chlorine. The Pd–P distances (2.314 (1) and 2.322 (1) A)
are similar to those in the palladium(II) phosphine com-
[Pd2(dba)3]
(dba5dibenzylideneacetone,
plexes [PdBr(3,5-F2C6H2CH=NC6H5)(PPh3)2] (2.32 3(3)
and 2.336(2) A) [5]. The Pd–C(1) distance (2.005(3) A) is
also similar to that found in the related complex (1a)
˚
˚
PhCH=CHC(O)CH=CHPh) [2], [3] and [PdClPh(dmphen)]
(dmphen52,9-dimethyl-1,10-phenanthroline), has recently
˚
˚
˚
been
prepared
by
reaction
of
[Pd(dimethyl-
(2.016(7) A), but the Pd–Cl distance in (2a) (2.4002(8) A)
maleate)(dmphen)] with PbPh2Cl2 [4].
is longer than that found in the complex (1a) (2.373(2) A)
[1]. These Pd–Cl distances are longer than those found in
the ion [PdCl4]22 (2.318 A), consistent with the trans
˚
influence of a phenyl group [6].
1. Results and discussion
The molecular structure of the complex (2d) is shown in
Fig. 2 which also gives the crystallographic numbering
scheme. Selected bond distances and angles are given in
Table 1. The geometry at the palladium in (2d) is square
planar. Pd–N bond distances (2.057(6)–2.121(6) A) are
similar to those in the complex [PdIPh(bipy)] (2.070(8)–
Exchange reactions of triphenylantimony in complexes
(1) with a variety of donor ligands in dichloromethane
˚
*
Corresponding author.
0277-5387/99/$ – see front matter
PII: S0277-5387(98)00404-5
1999 Elsevier Science Ltd. All rights reserved.

1142
A. Mentes et al. / Polyhedron 18 (1999) 1141–1145
Scheme 1.
Fig. 2. Molecular structure of 2d showing the atom numbering scheme.
Displacement parameters are shown at the 30% probability level.
Hydrogen atoms are omitted for clarity.
Scheme 2.
˚
2.144(8) A) [2]. The Pd–N(2) bond length in (2d)
˚
(2.121(6) A) is longer than the Pd–N(1) bond length
˚
(2.057(6) A), consistent with the trans influence of a
˚
phenyl group. The Pd–Cl bond distance (2.305(2) A) is
˚
similar to that reported for [PdPhCl(dmphen)] (2.306(1) A)
[4].
The reaction of [PdXPh(SbPh3)2] (X5Cl or Br) with
bis(diphenylphosphino) methane in dichloromethane af-
forded the dimeric s-phenyl complexes [PdXPh(dppm)]2.
The structure determinations of the compounds showed
them to be isostructural both being centrosymmetric
molecules. The geometry at palladium is square planar
with trans phosphorus donors and with each diphosphine
bridging to two palladium atoms. Selected bond distances
and angles are given in Table 2 for (3a) and (3b). The
molecular structures are shown in Figs. 3 and 4, respec-
tively. The Pd–P distances in complex (3a) (2.300(2) and
Fig. 1. Molecular structure of 2a showing the atom numbering scheme.
Displacement parameters are shown at the 30% probability level.
Hydrogen atoms are omitted for clarity.
˚
2.329(2) A) are similar to those found in
˚
[PdClMe(dppm)]2 (2.314(1) and 2.329(1) A) [7]. The
Table 1
Table 2
˚
˚
Selected bond distances [A] and bond angles [8] with estimated standard
Selected bond distances [A] and bond angles [8] with estimated standard
deviations in parenthesis for (2a) and (2d)
deviations in parenthesis for (3a) and (3b)
Complex (2a)
Complex (2d)
Complex (3a)
Complex (3b)
Bond distances
Bond distances
Bond distances
Bond distances
Pd–P(1)
Pd–P(2)
Pd–C(1)
Pd–Cl
2.3144(9)
2.3223(9)
2.005(3)
Pd–N(1)
Pd–N(2)
Pd–C(11)
Pd–Cl
2.057(6)
2.121(6)
1.970(7)
2.305(2)
Pd–P(1)
Pd–P(2)
Pd–C(11)
Pd–Cl
2.300(2)
2.329(2)
2.012(7)
2.427(2)
Pd–P(1)
Pd–P(2)
Pd–C(11)
Pd–Br
2.331(2)
2.306(2)
2.041(7)
2.5510(11)
2.4002(8)
Bond angles
Bond angles
Bond angles
Bond angles
P(1)–Pd–P(2)
P(1)–Pd–C(1)
P(2)–Pd–C(1)
Cl–Pd–P(1)
177.42(3)
N(1)–Pd–N(2)
N(1)–Pd–C(11)
N(2)–Pd–C(11)
N(1)–Pd–Cl
78.5(2)
94.1(3)
171.1(3)
173.7(2)
P(1)–Pd–P(2)
P(1)–Pd–C(11)
P(2)–Pd–C(11)
Cl–Pd–P(1)
167.09(6)
85.2(2)
90.0(2)
P(1)–Pd–P(2)
P(1)–Pd–C(11)
P(2)–Pd–C(11)
Br–Pd–P(1)
170.74(7)
88.6(2)
90.8(2)
94.231(6)
90.29(9)
91.50(9)
89.50(9)
92.90(6)

A. Mentes et al. / Polyhedron 18 (1999) 1141–1145
1143
2. Crystallography
Crystals of (2a), (2d), (3a) and (3b) suitable for X-ray
crystallographic analysis were grown from dichlorome-
thane/diethyl ether at room temperature. The crystal data,
a summary of the data collection and structure refinement
parameters are given in Table 3. Crystals were glued on
glass fibers. Unit cell dimensions were determined by least
squares refinement of optimised setting angles. The data
were corrected for Lorentz and polarisation effects, and
empirical absorption corrections were applied. The struc-
tures were solved by Patterson methods (SHELXTL PC)
[9], and refined by full matrix least squares using SHELXL
96 [10]. H atoms were included in calculated positions
˚
(C–H 0.96 A). All H atoms had isotropic displacement
parameters fixed at 1.2 Ueq of the bonded atom except
2
˚
those of (2a) for which U1150.05 A . All non H atoms
were refined with anisotropic displacement parameters.
Details of the X-ray structure determinations in the form of
ClF files for 2a, 2d, 3a and 3b have been deposited at the
Cambridge Crystallographic Data Centre. The deposition
numbers are 102989, 102990, 102991 and 102992, respec-
tively.
Fig. 3. Molecular structure of 3a showing the atom numbering scheme.
Displacement parameters are shown at the 30% probability level. Primed
atoms are generated by a centre of symmetry (symmetry code: 2x, 2y,
12z). Hydrogen atoms are omitted for clarity.
Pd–C and Pd–Cl distances in complex (3a) (2.012(7) and
3. Experimental
˚
2.427(2) A) are similar to those found in [PdClPh(Ph2
˚
SbCH2SbPh2)]2 (2.023(5) and 2.411(1) A) [8].
All reactions were performed under a dry, oxygen-free,
nitrogen atmosphere, using solvents which were dried and
distilled under nitrogen prior to use. Microanalysis were
carried out by Butterworth Laboratories Ltd., 54–56
Waldegrave Road, Teddington, Middlesex TW11 8LG.
Melting points were measured on a Reichert Hot stage
apparatus and are uncorrected. The FAB mass spectra of
the solid complexes were obtained on a Kratos Concept
The X-ray structure results show that the phenyl group
is always nearly perpendicular to the coordination plane
around palladium. Deviations from 908 are 20.58 (3b),
18.48 (2d), 14.58 (2a), and 8.48 (3a).
1
Double Focusing Sector Mass Spectrometer. The H NMR
spectra were recorded at room temperature in [2H1]
chloroform on a BRUKER ARX 250 spectrometer oper-
ating at 250.13 MHz with SiMe4 (0.0 ppm) as internal
reference. 13C–h1Hj NMR spectra were recorded at room
temperature in [2H1]chloroform on a BRUKER ARX 250
spectrometer operating at 62.9 MHz. The 31P–h1Hj NMR
spectra were recorded in CDCl3 on a BRUKER ARX 250
spectrometer operating at 23.1 MHz. The quoted IR
spectra were recorded on a Perkin-Elmer 580B spec-
trophotometer in Nujol mulls between polythene plates in
the range 600–200 cm21 or in Nujol mulls between NaCl
plates in the range 3000–600 cm21
.
The compounds [PdXPh(SbPh3)2 I (X5Cl or Br) were
prepared as described in the literature [1].
3.1. General procedure
Fig. 4. Molecular structure of 3b showing the atom numbering scheme.
Displacement parameters are shown at the 30% probability level. Primed
atoms are generated by a centre of symmetry (symmetry code: 12x, 12y,
12z). Hydrogen atoms are omitted for clarity.
An excess of the ligand (PPh3, AsPh3, bipy, dmbipy,
phen, dppm) in dichloromethane (2 cm3) was added to a
solution of [PdXPh(SbPh3)2] (0.1 g) in dichloromethane

1144
A. Mentes et al. / Polyhedron 18 (1999) 1141–1145
Table 3
Crystal data, data collection parameters and refinement details for 2a, 2d, 3a and 3b
Compound
2a
2d
3a
3b
Formula
Mol. wt.
Lattice
C42H35ClP2Pd
743.49
Orthorhombic
Pbca
11.818(2)
23.594(3)
25.397(3)
90
C16H13ClN2Pd
375.13
Monoclinic
P21 /c
9.439(3)
18.281(3)
8.738(2)
90
112.59(2)
90
C31H27ClP2Pd
603.32
Triclinic
P-1
10.181(4)
11.302(3)
12.473(5)
73.57(2)
75.79(3)
72.88(3)
1294.8(8) 2,
1.547
C31H27BrP2Pd
647.78
Triclinic
P-1
10.438(2)
11.709(2)
12.887(2)
72.78(1)
66.72(1)
66.63(1)
1309.9(4), 2
1.642
Space group
˚
a A
˚
b A
˚
c A
a8
b8
g8
90
90
3
˚
V A , Z
7082(2), 4
1.395
0.719
1392.1(6), 4
1.790
1.514
Dc Mg m3
m mm21
0.962
2.375
F(000)
3040
744
612
648
Cell refinement (reflections)
Crystal size mm
Crystal colour/shape
Scan range u8
Scan index limits (h, k, l)
Abs. correction T min, max
Data collected
36
26
40
21
0.5630.5030.46
Colourless block
2.5–25.0
21 13; 21 28; 21 30
0.739, 0.768
6941
0.3430.2030.07
Pale yellow plate
2.6–25.0
211 10; 221 1; 21 10
0.798, 0.912
3149
0.3130.2530.21
Yellow block
2.5–24.50
21
0.825, 0.878
4996
0.4430.1130.10
Yellow needle
2.8–25.0
11; 212 12; 214 14
0.863, 0.975
5439
Unique data
5652
1.034
0.0392, 4.37
0.0217
2444
1.023
0.031, 51.44
0.0408
4211
1.055
0.090, 3.79
0.0498
4610
1.028
0.0496, 1.29
0.0479
Goodness of fit on F2
a,ba in weighting scheme
R(int)
Observed data [F.4s(F)]
R1
4416
0.0332
1677
0.0508
3363
0.0563
2998
0.0561
wR2(all data)
0.0750
0.1164
0.1610
0.1363
Parameters n
DF e A
D/s
415
0.372, 20.406
0.002
181
1.098, 20.874
0.001
316
1.046, 21.061
0.001
316
0.673, 20.583
0.001
23
˚
˚
Details in common: Siemens P4 diffractometer monochromated Mo-Ka radiation (l50.7107 A) omega scans, 190 K.
R15oiFo2uFci/ouFou, wR25[w(F2o2F2c )2 /(Fo2)2]1 / 2, goodness of fit s5R[ow(Fo22F2c )2 /(n2p)]1 / 2 where n5number of reflections and p5total number of
parameters.
a w51/[s2(Fo2)1(aP)21bP] where P5(Fo25Fc2).
(8 cm) and the solution was refluxed for 4 h. The solution
was cooled to room temperature and diethyl ether or
hexane (10 cm3) was added. The filtered product was
washed with diethyl ether and dried in vacuo.
3.1.3. [PdClPh(AsPh3 )2 ], (2c).
1
Yield: 80 mg (89%), pale yellow solid. H NMR d5
7.36–7.18 (30H, m, Ph–As), 6.64–6.26 (5H, br, Ph–Pd).
FAB mass spectrum: m/z, 795 [M–Cl]1. IR.: 272 n(Pd–
Cl). M.p: 189–1908C (decomp.).
3.1.1. [PdClPh(PPh3 )2 ], (2a).
3.1.4. [PdClPh(bipy)], (2d)
Yield: 70 mg (88%) colourless crystals from CH2Cl2 /
hexane. (Found; C, 67.9; H, 4.6; Cl, 4.5. C42H35ClP2Pd
calc.; C, 67.8; H, 4.7; Cl, 4.5, %). 1H NMR, d57.49–7.19
(30H, m, Ph–P), 6.63 (2H, d, H2,6 –Ph), 6.37 (1H, t,
J514.5 Hz, H4 –Ph), 6.22 (2H, t, H3,5 –Ph). 31P–1hHj
NMR, 6523.86 (s) ppm. FAB mass spectrum: m/z, 707
[M–Cl]1. IR.: 280 n(Pd–Cl), cm21. M.p: 218–2228C
(decomp.).
Yield: 15 mg (37 %), pale yellow solid. (Found; C,
51.0; H, 3.3; N, 7.5. C18H13ClN2Pd, Calc.; C, 51.2: H, 3.5;
N, 7.5%). 1H NMR, d59.19 (1H, d, H4 –bipy), 8.04–7.88
(5H, m, H1,10, H2,9 and H7 –bipy), 7.48 (1H, m, H3 –bipy),
7.35 (2H, d, H12,16 –Ph), 7.23 (1H, m, H8 –bipy), 7.02–
6.88 (3H, m, H13,15 and H14 –Ph). FAB mass spectrum:
m/z, 339 [M–Cl]1 IR.: 1710, 1590, 1555 n(N=C), cm21
M.p: 223–2248C (decomp.).
.
3.1.2. [PdBrPh(PPh3 )2 , (2b)
Yield: 50 mg (61 %), flaky crystals from CH2Cl2 /
hexane. 1H NMR d57.61–7.13 (30H, m, Ph–P), 6.56 (2H,
d, H2,6 –Ph), 6.28 (1H, t, J514.2 Hz, H4 –Ph), 6.14 (2H, t,
H3,5 –Ph). 31P–1hHj NMR523.84 ppm (s). FAB mass
spectrum: m/z, 707 [M–Br]1. M.p: 2108C (decomp.).
3.1.5. [PdBrPh(bipy)], (2e)
1
Yield: 15 mg (35%), pale yellow solid. H NMR, d5
9.34 (1H, d, H4 –bipy), 8.04–7.88 (4H, m, H1,10 and H2,9),
7.82 (1H, d, H7 –bipy), 7.48 (1H, m, H3 –bipy), 7.35 (2H,
d, H12,16 –Ph), 7.23 (1H, m, H8 –bipy), 7.02–6.86 (3H, m,

A. Mentes et al. / Polyhedron 18 (1999) 1141–1145
1145
H13,15 – and H14 –Ph). FAB mass spectrum: m/z, 419
[M–Br]1. IR.: 1710, 1502, n(N=C), cm21. M.p: 220–
2228C (decomp.).
7.17 (40H, m, Ph–P), 6.65 (2H, br, H12,16 –Ph), 6.53 (1H,
m, J514.0 Hz, H14 –Ph), 6.45 (2H, m, H13,15 –Ph) 4.0 (4H,
br, CH2 ). 31P–1hHj NMR, d511.17 (s) ppm. FAB mass
spectrum: m/z, 1215 [M–Br]1. M.p: 184–58C (decomp.).
3.1.6. [PdClPh(dmbipy)], (2f)
Yield: 28 mg (64 %), pale yellow solid. H NMR,
1
d59.10 (1H, d, H4 –bipy), 7.86 (3H, m, H1,10 and H7),
7.42 (2H, d, H3,8 –bipy), 7.35 (2H, d, H14,18 –Ph), 7.10–
6.97 (3H, m, H15,17 and H16 –Ph), 2.53 (3H, s, Me), 2.48
(3H, s, Me). FAB mass spectrum: m/z, 367 [M–Cl]1. IR.:
1708, 1605, 1553, n(N=C), cm21. M.p: 269–2708C (de-
comp.).
Acknowledgements
We thank Zonguldak Karaelmas University, Turkey, for
financial support and Johnson Matthey plc for the loan of
palladium metal salts.
3.1.7. [PdClPh(phen)], (2g)
Yield: 28 mg (65 %), pale yellow solid. H NMR,
References
1
d59.49 (1H, dd, H2 –phen), 8.44 (2H, m, H4 – and H7 –
phen), 8.28 (1H, dd, H9 –phen), 7.95–7.81 (3H, m, H3 –
and H8 –phen, and H6 –phen), 7.58 (1H, m, H5 –phen), 7.47
(2H, d, H16,20 –Ph), 7.09–6.93 (3H, m, H17,19 and H18 –
Ph). FAB mass spectrum: m/z, 363 [M–Cl]1. R.: 1708,
1553, 1502 n(N=C), cm21. M.p: (decomp.).3008C.
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3.1.8. [PdClPh(dppm)]2 , (3a)
Yield: 45 mg (71 %), pale yellow solid. H NMR,
´
[5] J. Albert, J. Granell, R. Moragas, J. Sales, M. Font-Bardıa, X.
1
Solans, J. Organomet. Chem. 494 (1995) 95.
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5744.
d57.75–7.03 (40H, m, Ph–P), 6.75 (2H, br, H12,16 –Ph),
6.68 (1H, m, J514.2 Hz, H14 –Ph), 6.55 (2H, m, H13,15
–
Ph), 3.86–3.6 (4H, br, CH2 ). 31P–1hHj NMR, d510.5 (s)
ppm. FAB mass spectrum: m/z, 1171 [M–Cl]1. IR.: 280
n(Pd–Cl), cm21. M.p: 196–2008C (decomp.).
[8] A.F. Chiffey, J. Evans, W. Levason, M. Webster, Organometallics 14
(1995) 1522.
[9] G.M. Sheldrick SHELXTL PC, Release 4.2, Siemens Analytical
X-Ray Instruments, Madison, WI, 1991.
[10] G.M. Sheldrick, SHELXL 96, Program for Crystal Structure Refine-
3.1.9. [PdBrPh(dppm)]2 , (3b)
Yield: 46 mg (69%) pale yellow crystals from CH2Cl2 /
hexane. (Found; C, 56.6; H, 4.3; Br, 12.4. C62H54Br2P4Pd2
¨
ment, University of Gottingen, 1996.
1
calc.; C, 57.5; H, 4.2; Br, 12.4, %). H NMR, d57.35–