C4H3SSeCH2CH2OC6 H5: Synthesis, characterization and reaction with palladium(II) and nickel(II)

Article abstract of DOI:10.1016/S0022-328X(03)00450-9

ThSeCH₂CH₂OPh (Th=2-thienyl, C₄H₃S-; Ph=phenyl) (2) has been prepared by the reaction of BrCH₂CH₂OPh (1) and ThSeLi. The compound was characterized by ¹³C{¹H}- and ⁷⁷Se-NMR spectroscopy and X-ray crystallography. 2 is monoclinic, space group P 2₁/c, a=10.865(2), b=5.152(1), c=41.996(8) ?, β=92.20(3)°. All bond lengths and angles are quite normal as exemplified by the respective Se-C(alkyl) and Se-C(aryl) bonds of 1.957(6)-1.966(6) and 1.901(7)-1.905(7) ?. The lattice is composed of discrete molecules that are joined together by weak hydrogen bonds into a three-dimensional network. Upon treating ThSeCH₂CH₂OPh with [PdCl₂ (NCPh)₂] and [NiCl₂(PPh₃)₂] in benzene, a dinuclear palladium complex [Pd₂Cl₂ (μ-Cl)(μ-SeTh)(PPh₃)₂] (3) and a mononuclear complex [PdCl₂(PPh₃)₂] (4) were formed together with a precipitation of NiCl₂. The X-ray quality crystals were recrystallized in CH₂Cl₂. 3·2.5CH₂Cl₂ is monoclinic, space group C2/c, a=32.907(7), b=14.545(3), c=22.433(5) ?, β =114.37(3)° and contains a novel asymmetrical arrangement of one bridging chlorido and thienylselenolato ligand. Both palladium atoms show an square-planar coordination. The terminal Pd-Cl bond lengths are 2.388(1) and 2.346(1) ? with slightly longer distances of 2.418(1) and 2.450(1) ? involving the bridging chlorido ligand. The Pd-Se distances are 2.4092(9) and 2.4376(7) ?.

Full text of DOI:10.1016/S0022-328X(03)00450-9

Journal of Organometallic Chemistry 678 (2003) 95ꢁ101
/
www.elsevier.com/locate/jorganchem
C4H3SSeCH2CH2OC6H5: synthesis, characterization and reaction
with palladium(II) and nickel(II)
Raija Oilunkaniemi a,*, Risto S. Laitinen a, Milja S. Hannu-Kuure a, Markku Ahlgre´n b
a Department of Chemistry, University of Oulu, P.O. Box 3000, FIN-90014 Oulu, Finland
b Department of Chemistry, University of Joensuu, P.O. Box 111, FIN-80101 Joensuu, Finland
Received 7 March 2003; received in revised form 13 May 2003; accepted 14 May 2003
Abstract
ThSeCH2CH2OPh (Thꢀ
/
2-thienyl, C4H3S-; Phꢀphenyl) (2) has been prepared by the reaction of BrCH2CH2OPh (1) and
/
ThSeLi. The compound was characterized by 13C{1H}- and 77Se-NMR spectroscopy and X-ray crystallography. 2 is monoclinic,
˚
space group P21/c, aꢀ
exemplified by the respective Seꢀ
/
10.865(2), bꢀ
/
5.152(1), cꢀ
/
41.996(8) A, bꢀ
/
92.20(3)8. All bond lengths and angles are quite normal as
˚
/
C(alkyl) and Seꢀ
/
C(aryl) bonds of 1.957(6)ꢁ
/
1.966(6) and 1.901(7)ꢁ1.905(7) A. The lattice is
/
composed of discrete molecules that are joined together by weak hydrogen bonds into a three-dimensional network. Upon treating
ThSeCH2CH2OPh with [PdCl2(NCPh)2] and [NiCl2(PPh3)2] in benzene, a dinuclear palladium complex [Pd2Cl2(m-Cl)(m-
SeTh)(PPh3)2] (3) and a mononuclear complex [PdCl2(PPh3)2] (4) were formed together with a precipitation of NiCl2. The X-ray
quality crystals were recrystallized in CH2Cl2. 3×
/
2.5CH2Cl2 is monoclinic, space group C2/c, aꢀ
/
32.907(7), bꢀ
/
14.545(3), cꢀ
/
˚
22.433(5) A, bꢀ
/
114.37(3)8 and contains a novel asymmetrical arrangement of one bridging chlorido and thienylselenolato ligand.
˚
Cl bond lengths are 2.388(1) and 2.346(1) A with
Both palladium atoms show an square-planar coordination. The terminal Pdꢀ
/
˚
slightly longer distances of 2.418(1) and 2.450(1) A involving the bridging chlorido ligand. The Pdꢀ
/Se distances are 2.4092(9) and
˚
2.4376(7) A.
# 2003 Elsevier B.V. All rights reserved.
Keywords: 2-Phenoxyethylthienylselenide; Palladium complex; X-ray crystallography; NMR spectroscopy
1. Introduction
selenium donor and to another Pd(II) center involving
the p-electrons of the terminal Cꢁ bond [6].
/C
Selenoethers contain a soft donor atom and can
therefore easily coordinate with soft transition metal
centers such as palladium and platinum, and there is a
number of reports on the formation and structural
characterization of complexes containing mono- and
[PtCl2(PhSeCH2CH2NMe2)] contains a chelating ligand
coordinating both through a selenium and a nitrogen
donor [7]. The tridentate ligand in chlorido{(4-methyl-2-
phenylselenyl)phenylazo-p-toluene}palladium involves
a selenium, nitrogen and Cꢂ donor in the coordination
[8].
polyselenoethers (for recent reviews, see Refs. [1ꢁ
/
5] and
references therein).
There are only a very few reports on the hybrid
complexes containing different Group 16 donor atoms.
In fact, there are examples that the selenium-containing
crown ethers coordinate only through selenium and not
The solid state structural chemistry of hybrid poly-
dentate selenoether complexes of palladium and plati-
num is very sparse (for the most recent review, see Ref.
[5]). The two platinum atoms in [(PtMe2)2{m-(H2Cꢁ
CHꢀCH2ꢀCH2)2Se}] are bridged by the selenoether
ligand that coordinates to one Pt(II) center through a
/
through the ether oxygen atom [9ꢁ11]. One of the very
/
/
/
few examples exhibiting simultaneous selenium and
oxygen coordination is [Pd(Ph)(PPh3)(MeSeCH2COO)]
[12].
The lightest metal of the Group 10 elements, nickel,
shows very few selenoether complexes. X-ray structures
have only been established for [NiCl2(MeSeCH2CH2-
* Corresponding author. Tel.: ꢃ
1608.
/
358-8-553-1686; fax: ꢃ358-8-553-
/
E-mail address: raija.oilunkaniemi@oulu.fi (R. Oilunkaniemi).
0022-328X/03/$ - see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00450-9

96
R. Oilunkaniemi et al. / Journal of Organometallic Chemistry 678 (2003) 95ꢁ101
/
SeMe)]2 [13] and [{C5H3N)CH2SeCH2-N,Se}2(OH2)2-
MeNO2 [14] that both exhibit an octahedral
coordination around nickel.
[1C; C(n1)]; 128.1 [1C; C(n3)]; 129.5 [2C; C(n13),
C(n15)]; 131.0 [1C; C(n2)]; 136.2 [1C; C(n4)]; 158.3
Ni][ClO4]×
/
ppm [1C; C(n11)] (nꢀ
/
1 or 2; for numbering of the
The goal of the present contribution was to explore
atoms, see Fig. 2).
whether a hybrid selenoether ligand containing a Cꢀ
/
Oꢀ
/
C moiety could be utilized as a bridging ligand in the
formation of a heteronuclear complex containing Group
10 metals nickel and palladium. In this paper we report
the preparation and structural characterization of
2.3. Complexation of ThSeCH2CH2OPh with Pd(II)
and Ni(II)
ThSeCH2CH2OPh (2) (51 mg, 0.18 mmol) was
dissolved in 5 ml of benzene and the resulting solution
was added into 5 ml of a benzene solution containing 32
mg (0.083 mmol) of [PdCl2(PhCN)2]. Subsequently, 53
mg (0.081 mmol) of [NiCl2(PPh3)2] in 5 ml of benzene
was added into the reaction mixture. The pale green
precipitate was filtered off and the solution was con-
centrated by evaporation upon stirring overnight during
which a yellow precipitate was formed. After filtration,
the raw product was recrystallized from dichloro-
ThSeCH2CH2OPh (Thꢀ2-thienyl, C4H3S) as well as
/
some of its ligand properties. The X-ray structure of
PhOCH2CH2Br that is one of the starting materials in
the synthesis of ThSeCH2CH2OPh has been reported for
comparison.
2. Experimental
2.1. General
methane. Crystals of [Pd2Cl2(m-Cl)(m-SeTh)(PPh3)2]×
2.5CH2Cl2 (3×2.5CH2Cl2) and [PdCl2(PPh3)2]×2CH2Cl2
(4×2CH2Cl2) were separated from the solid mixture
under a microscope and identified by X-ray crystal-
lography. NMR (298 K, CH2Cl2): 31P{1H} dꢀ
33.9
ppm (3), dꢀ24.0 ppm (4).
/
/
/
PhOCH2CH2Br (1, Aldrich), n-butyllithium (2.5 M
solution in hexanes, Aldrich), thiophene (Riedel de
Haen, dried and distilled prior to use), selenium
(granules, Merck), and NiCl2 (Merck) were commer-
cially available. [PdCl2(PhCN)2] was synthesized by
modifying the method of Kharasch et al. [15] and
[NiCl2(PPh3)2] by the method of Venanzi [16].
/
/
/
2.4. NMR spectroscopy
The NMR spectra were recorded on a Bruker DPX
400 operating at 100.61, 76.31 and 161.98 MHz for
13C{1H}, 77Se and 31P{1H}, respectively. Saturated
solution of SeO2 (aq) was used as an external standard
for the 77Se spectra and H3PO4 (85%) was used as an
external standard for the 31P spectra. Chemical shifts
(ppm) are reported relative to Me4Si, neat Me2Se and
2.2. Preparation of ThSeCH2CH2OPh (2)
n-BuLi (2.5 M, 6.00 ml; 15.0 mmol) was added into a
solution of 1.5 ml (17.0 mmol) of thiophene in 25 ml of
tetrahydrofuran that was cooled in an ice bath. The
mixture was stirred at room temperature (r.t.) for 1 h.
Powdered selenium (1.35 g; 17.0 mmol) was added to the
solution under a nitrogen flow and the mixture was
stirred at r.t. for an additional hour. PhOCH2CH2Br
(3.44 g, 17.0 mmol) was gradually added into the
reaction mixture in small portions. After 30 min the
reaction mixture was poured into water (150 ml), the
H3PO4 (85%). {d(Me2Se)ꢀ
/
d(SeO2)ꢃ1302.6) [17]}.
/
2.5. X-ray crystallography
Diffraction data of 1, 2, 2.5CH2Cl2 and 4×
were collected on a Nonius Kappa CCD diffractometer
at 150 K using graphite monochromated MoꢁKa
0.71073 A). Crystal data and the details
/2CH2Cl2
product was extracted in dichloromethane (3ꢄ50 ml),
/
and the organic layer was dried with MgSO4. The yield
of ThSeCH2CH2OPh in the product mixture was ca.
85% (based on selenium), as judged by the 77Se-NMR
spectrum recorded in the CH2Cl2 solution. The solvent
was removed upon evaporation and the oily residue was
/
˚
radiation (lꢀ
/
of structure determination are given in Table 1.
Structures were solved by direct methods using
SHELXS-97 [18] and refined using SHELXL-97 [19]. The
thienyl rings in 2 were found to be disordered. The
disorder was taken into account by refining the site
occupation factors of the two alternative orientations
and constraining their sums to unity. Because the
thermal parameters of the disordered atoms correlate
with the site occupation factors, the thermal parameters
of the disordered pairs of atoms were restrained to be
equal.
dissolved in hexane and cooled to ꢂ208. The resulting
/
pale yellow precipitate was filtered cold, washed several
times with cold hexane, and dried. Small colourless
crystals were obtained from ethanol by slow evaporation
of the solvent. Yield of the purified product: 2.31 g
(54%). Anal. calc. for C12H12OSSe: C 50.88, H 4.27, S
11.32; found: C 49.86, H 4.04, S 10.89%. NMR (298 K,
2
3
CH2Cl2): 77Se dꢀ
183 ppm, JSeꢀH 15.2 Hz, JSeꢀH 5.1
/
Hz; 13C{1H}: 29.4 [1C; C(n18)]; 67.0 [1C; C(n17)];
114.6 [2C; C(n12), C(n16)]; 120.9 [1C; C(n14)]; 122.7
After the full-matrix least-squares refinement of the
non-hydrogen atoms with anisotropic thermal para-

R. Oilunkaniemi et al. / Journal of Organometallic Chemistry 678 (2003) 95ꢁ
/
101
97
Table 1
Details of the structure determination of PhOCH2CH2Br (1), ThSeCH2CH2OPh (2), [Pd2Cl2(m-Cl)(m-SeTh)(PPh3)2] (3) and trans-[PdCl2(PPh3)2] (4)
1
2
3×
/
2.5CH2Cl2
4×
/
2CH2Cl2
Empirical formula
Relative molecular mass
Crystal system
C8H9BrO
201.06
C24H24O2S2Se2
283.24
C42.5H38Cl8P2SSePd2 C19H17Cl3PPd0.5
1218.09
Monoclinic
C2/c
435.85
Orthorhombic
Pbca
Monoclinic
C2/c
Monoclinic
P21/c
Space group
Unit cell dimensions
˚
a (A)
19.049 (4)
5.478(1)
15.536(3)
98.79(3)
1602.1(6)
8
10.865(2)
5.1522(1)
41.996(8)
92.20(3)
2349.1(8)
4
32.907(7)
14.545(3)
22.433(5)
114.37(3)
9781(3)
8
20.122(4)
7.994(2)
23.032(5)
˚
b (A)
˚
c (A)
b (8)
3
˚
V (A )
3705(1)
8
Z
F(0 0 0)
Dcalc (g cmꢂ3
800
1.667
5.058
1136
1.602
3.344
4808
1.654
2.055
1760
1.563
1.048
)
m(Moꢁ
/
Ka) (mmꢂ1
Crystal size (mm)
)
0.20ꢄ
/
0.12ꢄ
/
0.10 0.35ꢄ
/
0.15ꢄ
/
0.08 0.20ꢄ
/
0.15ꢄ/0.12
0.15ꢄ
/
0.12ꢄ0.10
/
u range (8)
3.16ꢁ25.98
/
3.01ꢁ25.00
/
2.33ꢁ/26.00
2.69ꢁ29.13
/
Number of reflections collected
Number of unique reflections
Number of observed reflections a
Number of parameters/restraints
Rint
2951
1569
1464
92/0
11555
3819
2970
42763
8789
6430
549/5
38631
4726
3614
215/0
274/20
0.0839
0.0561
0.1413
0.0750
0.1543
1.101
0.0160
0.0340
0.1098
0.0363
0.1135
1.016
0.0412
0.0358
0.0712
0.0597
0.0799
1.027
0.0534
0.0337
0.0762
0.0549
0.0847
1.024
b
R1
b
wR2
R1 (all data)
wR2 (all data)
Goodness-of-fit on F2
ꢂ3
˚
Max/min heights in final difference Fourier synthesis (e A
)
0.557, ꢂ
/0.728
0.514, ꢂ
/
0.622
0.824, ꢂ
/0.699
0.688, ꢂ0.921
/
a
I ꢀ
R1ꢀ
/
2s(I).
b
2
2 2
2
2 21
//
/
ajjFo jꢂ
/
jFc jj/ajFo j, wR2ꢀ
/
[aw(jFo j ꢂjFc j ) /aw(Fo ) ].
/
meters, the hydrogen atoms were placed in calculated
˚
0.95 A and in
in an analogous reaction when treating FuSeLi (Fuꢁ
/
positions in the aromatic rings (Cꢀ
/
Hꢀ
/
C4H3O, furyl) with PhOCH2CH2Br [22]. The broad
singlet at 258 ppm is assigned to Th2Se based on the
well-established relationship between the 77Se and 125Te
˚
0.99 A). The scattering factors
for the neutral atoms were those incorporated with the
programs.
the CH2 groups (Cꢀ
/
Hꢀ
/
chemical shifts in analogous compounds [23ꢁ26] and on
/
the known 125Te chemical shift of Th2Te at 402 ppm
[27]. The quintet at 289 ppm (2JSeꢀH
to (PhOCH2CH2)2Se.
ꢀ16 Hz) is assigned
/
3. Results and discussion
3.2. Crystal structures
3.1. Preparation of ThSeCH2CH2OPh (2)
The reaction of BrCH2CH2OPh (1) with ThSeLi in
THF produced ThSeCH2CH2OPh (2) in a good yield.
The 77Se-NMR spectrum of the reaction mixture shows
a major resonance at 183 ppm together with minor
resonances at 492, 459, 323, 289 and 258 ppm.
3.2.1. BrCH2CH2OPh (1) and ThSeCH2CH2OPh (2)
The molecular structures of PhOCH2CH2Br (1) and
ThSeCH2CH2OPh (2) indicating the numbering of the
atoms are shown in Figs. 1 and 2 together with the
selected bond lengths and angles.
The isolated and purified ThSeCH2CH2OPh shows
only one resonance at 183 ppm that appears as a triplet
Both compounds show quite normal bond para-
meters. The PhOCC frameworks in 1 and 2 are
approximately planar and show a similar conformation.
It is interesting to note that while Br(1) in 1 deviates
3
of triplets (2JSeꢀH
ꢀ
/
15.2 Hz, JSeꢀH
ꢀ5.1 Hz). The
/
assignment of the ten 13C chemical shifts of purified
ThSeCH2CH2OPh has been based on those from
BrCH2CH2OPh (1) [20] and Th2Se2 [21].
from this plane [the torsional angle O(1)ꢀ
/
C(7)ꢀ
/
C(8)ꢀ
/
Br(1) is 68.5(2)8; for numbering of atoms, see Fig. 1], the
corresponding selenium atoms Se(11) and Se(21) in 2 lie
The minor resonance at 492 ppm is due to Th2Se2 [21]
and the triplet at 459 ppm (2JSeꢀH
to (PhOCH2CH2Se)2 that has previously been isolated
ꢀ/15.9 Hz) is assigned
approximately on the plane (the torsional angles O(n1)ꢀ
/
C(n17)ꢀC(n18)ꢀSe(n1) are 173.9(4) and 174.1(4)8; for
/
/

98
R. Oilunkaniemi et al. / Journal of Organometallic Chemistry 678 (2003) 95ꢁ101
/
Fig. 3. The two possible orientations of the X group in PhOCH2CH2X
(XꢀBr and SeTh) due to steric requirements. The 2p lone pair orbital
of the oxygen atom is indicated in the figure. Its minimized repulsion
with the p-electrons of the phenyl ring requires a planar PhOCC
framework.
/
Fig. 1. The molecular structure of PhOCH2CH2Br (1) indicating the
numbering of atoms. The thermal ellipsoids have been drawn at 50%
˚
probability level. Selected bond lengths (A) and angles (8): C(1)ꢀ
/
O(1)
Br(1) 1.960(3);
C(8) 107.6(2); C(7)ꢀC(8)ꢀBr(1)
1.373(3); O(1)ꢀ
C(1)ꢀO(1)ꢀC(7) 117.5(2); O(1)ꢀ
111.0(2).
/
C(7) 1.430(3); C(7)ꢀ
/
C(8) 1.502(3); C(8)ꢀ
/
/
/
/
C(7)ꢀ
/
/
/
exhibits the former orientation and the selenium atoms
in 2 the latter.
The thienyl groups in both independent molecules of
2 are disordered. The more abundant orientations with
site occupation factors of 62.4(9) and 55.1(8)% for
molecules 1 and 2, respectively, are shown in Fig. 2. In
both molecules the thienyl ring is almost perpendicular
to the Se(n1)ꢀ
/
C(n18) bond. The angles between the
planes of thienyl groups and the Se(n1)ꢀ
/C(n18) bonds
in the two molecules are 75.7(2) and 70.8(2)8 in
qualitative agreement with the values 86.2 and 85.08
between the plane of the aromatic ring and Seꢀ
/Se bonds
in Th2Se2 and Fu2Se2 [21]. In diselenides, however, the
magnitude of this angle is dependent on the electronic
and steric factors of the aromatic ring (see discussion
and reference in Ref. [21]).
The molecules in both 1 and 2 are joined together into
a continuous three-dimensional network by weak hy-
drogen bonds, as shown in Fig. 4. The shortest H/
ꢀ ꢀ ꢀ
/
O
Fig. 2. The two molecules of PhOCH2CH2SeTh (2) in the asymmetric
unit indicating the numbering of atoms. The thermal ellipsoids have
contacts show values of 2.660(2) and 2.671(4)ꢁ2.693(4)
/
˚
A for 1 and 2, respectively. In addition, there are short
contacts in both 1 and 2 involving the interaction
between the methylene hydrogen atoms and the p-
electrons of the phenyl rings.
˚
been drawn at 50% probability level. Selected bond lengths (A) and
angles (8): C(n11)ꢀO(n1) 1.376(7), 1.372(7); O(n1)ꢀC(n17) 1.441(7),
1.450(7); C(n17)ꢀC(n18) 1.507(8), 1.509(9); C(n18)ꢀSe(n1) 1.957(6),
1.966(6); Se(n1)ꢀC(n1A/B) 1.901(7), 1.905(7); C(n11)ꢀO(n(1)ꢀC(n17)
118.5(4), 117.9(4); O(n1)ꢀC(n17)ꢀC(n18) 104.6(5), 104.7(5); C(n17)ꢀ
C(n18)ꢀSe(n1) 113.0(4), 111.6(4): C(n18)ꢀSe(n1)ꢀC(n1A/B) 96.6(3),
96.2(3). The first value in each pair refers to molecule 1 (nꢀ1) and the
second value to molecule 2 (nꢀ2).
/
/
/
/
/
/
/
/
/
/
/
/
/
/
3.2.2. cis-[Pd2Cl2(m-Cl)(m-SeTh)(PPh3)2] (3) and
trans-[PdCl2(PPh3)2] (4)
/
The molecular structure and the numbering of the
atoms of [Pd2Cl2(m-Cl)(m-SeTh)(PPh3)2] (3) is shown on
Fig. 5. The crystal structure of 3 is the first example of
the asymmetric selenolato- and chlorido-bridged dipal-
ladium structure. The syntheses and NMR data for the
numbering of atoms, see Fig. 2). The planarity of the
PhOCC fragment and the two possible orientations of
the X atom bonded to it (XꢀBr or Se) can be explained
/
by steric and electronic factors, as shown in Fig. 3. One
of the oxygen lone-pairs is in a 2p orbital and
similar complexes have been reported previously [28ꢁ
/
necessitates the Cꢀ
/
Oꢀ
/
CꢀC torsional angle of ca. 08
/
31], but X-ray structures are known neither for palla-
dium nor the related platinum complexes. The sulfur
analogues of the palladium complexes form a better
for minimized repulsion between these lone-pair elec-
trons and the p-electrons of the phenyl ring. Further,
there are two possible orientations for the CH2X group
to be staggered with respect to the CH2O group that is
directly bonded to it. One leads to the OCCX torsional
angle of ca. 608 and the other to the torsional angle of
ca. 1808, as indicated in Fig. 3. The bromine atom in 1
explored series [32ꢁ
The lattice of
2.5CH2Cl2 (3×2.5CH2Cl2) is composed of planar discrete
/
35].
[Pd2Cl2(m-Cl)(m-SeTh)(PPh3)2]×
/
/
dinuclear complexes with the terminal chlorido-ligands
in cis-positions with respect to each other. Selected bond

R. Oilunkaniemi et al. / Journal of Organometallic Chemistry 678 (2003) 95ꢁ
/
101
99
trans-influence of Clꢂ-ligand compared to those of
RSeꢂ and Ph3P. The terminal Pdꢀ
Cl bonds are also
shorter than the bridging PdꢀCl bonds. These bond
lengths are comparable to the bridging and terminal
/
/
Pdꢀ
/
Cl bonds in m-thiolato complexes [Pd2Cl2(m-Cl)( m-
?
SR)(PR2Rƒ)2] (Rꢀ
/
Et; R?ꢀ
/
Me; Rƒꢀ
/
Ph [32]; Rꢀ
/Me,
t-Bu, Ph; R?ꢀ
/
RƒꢀMe [34]).
/
The crystal and molecular structure of 4×
/2CH2Cl2 was
determined in order to assign the 31P{1H} resonance at
24.0 ppm. The structural features of [PdCl2(PPh3)2]
crystallized from different solvents have been reported
for several times [38ꢁ
al. [42] described the structure of exactly the same
crystalline phase 4×2CH2Cl2, as we have observed in this
work (see Table 2).
/42]. A recent report by Vicente et
/
3.3. Ligand chemistry of ThSeCH2CH2OPh
When ThSeCH2CH2OPh (2) was treated with a
benzene solution of [PdCl2(PhCN)2] and a solution of
[NiCl2(PPh3)2] was subsequently added into the reaction
mixture (the molar ratio of the reactants was ca. 2:1:1),
the red colour of the solution disappeared and the
solution became yellow. At the same time a pale green
precipitate of NiCl2 was obtained. The 31P{1H}-NMR
spectrum of the reaction solution showed two reso-
nances at 33.9 and 24.0 ppm. Upon recrystallization
from dichloromethane, crystals of [Pd2Cl2(m-
Cl)(mSeTh)(PPh3)2]×
/
2.5CH2Cl2
(3×
/
2.5CH2Cl2)
and
[PdCl2(PPh3)2]×
/
2CH2Cl2 (4×2CH2Cl2) were obtained.
/
Fig. 4. Hydrogen bonding network in (a) BrCH2CH2OPh and (b)
ThSeCH2CH2OPh.
The redissolved crystals indicated that the 31P{1H}
resonance at 33.9 ppm is due to 3 and that at 24.0
ppm is due to 4.
The addition of ThSeCH2CH2OPh results in the
substitution of the PhCN ligands in [PdCl2(NCPh)2]
and formation of [PdCl2{Se(Th)CH2CH2OPh}2] (5), as
inferred by the observation of the 77Se resonance at 268
ppm in the NMR spectrum of the reaction solution at
this stage {c.f. d(77Se)ꢀ
233 ppm observed for
/
[PdCl2(SeMeTh)2] [43]}. The 13C{1H} spectrum showed
resonances at 36.7 [1C; C(n18)], 63.8 [1C; C(n17)],
114.7 [2C; C(n12), C(n16)], 120.3 [1C; C(n14)], 121.4
[1C; C(n1)], 127.9 [1C; C(n3)], 129.5 [2C; C(n13),
C(n15)], 132.9 [1C; C(n2)], 136.2 [1C; C(n4)] and
157.9 ppm [1C; C(n11)]. They can be interpreted in
terms of a ThSeCH2CH2OPh ligand coordinated to
palladium. The resonance at 36.7 ppm due to C(n18) has
shifted 7.4 ppm downfield from the corresponding
resonance in free 2. Similar downfield shift of 6 ppm
has been observed for the methyl carbon in the case of
coordination of ThSeMe to palladium in [PdCl2(Se-
MeTh)2] [43]. The resonance at 120.3 ppm due to the
quaternary carbon in the thienyl ring C(n1) has shifted
2.4 ppm upfield from the corresponding resonance in 2
in agreement with the upfield shift of 2 ppm observed
Fig. 5. The molecular structure of cis-[Pd2Cl2(m-Cl)(m-SeTh)(PPh3)2]
(3) indicating the numbering of atoms. The thermal ellipsoids have
been drawn at 50% probability level.
lengths and angles are listed in Table 2. Both palladium
atoms show a slightly distorted square-planar coordina-
tion geometry [the sums of bond angles are 360.13(5)
and 360.08(4)8 for Pd(1) and Pd(2), respectively]. The
terminal Pdꢀ
/
Se bond lengths are slightly smaller
Se distances in [Pd2(m-
than the bridging Pdꢀ
/
SeTh)2(SeTh)2(PPh3)2] [36] and [Pd2(m-SePh)2(SePh)2-
(PPh3)2] [37]. This is consistent with the slightly weaker

100
R. Oilunkaniemi et al. / Journal of Organometallic Chemistry 678 (2003) 95ꢁ
/
101
Table 2
˚
Selected bond lengths [A] and angles [8] for cis-[Pd2Cl2(m-Cl)(m-SeTh)(PPh3)2] (3) and trans-[PdCl2(PPh3)2] (4)
cis-[Pd2Cl2(m-Cl)(m-SeTh)(PPh3)2] (3)
Bond lengths Bond angles
trans-[PdCl2(PPh3)2] (4)7(7)
Bond lengths
Bond angles
Pd(1)ꢀ
Pd(1)ꢀ
Pd(1)ꢀ
Pd(1)ꢀ
Pd(2)ꢀ
Pd(2)ꢀ
Pd(2)ꢀ
Pd(2)ꢀ
Se(1)ꢀ
/
Se(1)
Cl(1)
Cl(3)
P(1)
2.4376(7)
2.388(1)
2.418(1)
2.243(1)
2.4092(9)
2.346(1)
2.450(1)
2.275(1)
1.936(4)
Se(1)ꢀ
Se(1)ꢀ
Se(1)ꢀ
Cl(1)ꢀ
Cl(1)ꢀ
Cl(3)ꢀ
Se(1)ꢀ
Se(1)ꢀ
Se(1)ꢀ
Cl(2)ꢀ
Cl(2)ꢀ
Cl(3)ꢀ
Pd(1)ꢀ
Pd(1)ꢀ
Pd(1)ꢀ
Pd(2)ꢀ
/
Pd(1)ꢀ
Pd(1)ꢀ
Pd(1)ꢀ
Pd(1)ꢀ
Pd(1)ꢀ
Pd(1)ꢀ
Pd(2)ꢀ
Pd(2)ꢀ
Pd(2)ꢀ
Pd(2)ꢀ
Pd(2)ꢀ
Pd(2)ꢀ
Se(1)ꢀ
Cl(3)ꢀ
Se(1)ꢀ
Se(1)ꢀ
/
Cl(1)
Cl(3)
P(1)
177.27(3)
85.71(4)
92.99(4)
93.52(5)
87.92(5)
176.75(4)
177.89(3)
85.71(4)
94.59(4)
92.66(5)
87.12(5)
179.74(4)
94.57(3)
94.02(5)
100.9(1)
99.9(1)
Pd(1)ꢀ
Pd(1)ꢀ
/
Cl(1)
P(1)
2.2997(7)
2.3247(6)
Cl(1)ꢀ
Cl(1)ꢀ
Cl(1)ꢀ
P(1)ꢀPd(1)ꢀ
/
Pd(1)ꢀ
Pd(1)ꢀ
Pd(1)ꢀ
/
P(1)
Cl(1) a
P(1) a
93.36(2)
180.0
/
/
/
/
/
/
/
/
/
/
/
86.64(2)
180.0
/
/
/Cl(3)
/
/
P(1) a
/
Se(1)
Cl(2)
Cl(3)
P(2)
/
/P(1)
/
/
/P(1)
/
/
/
Cl(2)
Cl(3)
P(2)
/
/
/
/
C(11)
/
/
/
/Cl(3)
/
/P(2)
/
/P(2)
/
/
Pd(2)
Pd(2)
C(11)
C(11)
/
/
/
/
/
/
a
Symmetry operation: 1ꢂ
/
x, y, 1ꢃz.
/
for ThSeMe [43]. Other resonances of 2 are not affected
by the coordination.
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