Synthesis and reactions of mono- and dipalladium complexes containing 2-thienyl and 2,5 (or 2,5′) -bridged thienylene (or dithienylene) ligand: New dipalladium complex formation connected by thioketene part via C-S bond cleavage of thiophene

Article abstract of DOI:10.1016/S0022-328X(99)00391-5

Oxidative addition reactions of 2-iodothiophene, 2-bromothiophene, and 2,5-dibromothiophene with equimolar Pd(CH₂=CHPh)L₂ (L=PMe₃ and PEt₃) at room temperature in THF produce mononuclear σ-thienyl palladium(II) complexes trans-(2-C₄H₃S)PdX(PMe₃)₂ (X=I, 1; X=Br, 2) and trans-(5-Br(2-C₄H₂S))PdBrL₂ (L=PMe₃, 3; L=PEt_3, 4). Reactions using 2,5-dibromothiophene, 2,5-diiodothiophene, and 5,5-dibromo-2,2′-bithiophene under 2:1 molar ratio in THF give thienylene (or dithienylene) bridged dipalladium complexes trans,trans-L₂XPd(μ-2,5-C₄H₂S)PdXL ₂ (L=PMe₃; X=I, 5; Br, 6; L=PEt₃; X=Br, 7) and trans,trans-(Me₃P)₂BrPd(μ-2,5′-C ₄H₂S-C₄H₂S)PdBr(PMe ₃)₂ (8), in high yields. However, the equimolar reaction of 2,5-dibromothiophene with the Pd(0) complex results in formation of a dinuclear complex cis,trans-[(Me₃P)₂Pd(η ²-S=C=CH-CH=CBr)PdBr(PMe₃)₂ (9), in 56% yield via C-S bond cleavage of the thiophene ring. All the complexes provided satisfactory IR and NMR (¹H, ³¹P{¹H}, and ¹³C{¹H}) spectra as well as elemental analyses. Molecular structures of 1, 7, and 9 were confirmed by X-ray crystallography. Treatment of 5 and 7 with CO (1 atm) results in CO insertion into one of the Pd-C bonds to give trans,trans-(Me₃P)₂IPdC(O)C₄H ₂SPdI(PMe₃)₂ (10) in 94% and trans,trans-(Et₃P)₂BrPdC(O)C₄H ₂SPdBr(PEt₃)₂ (11) in 23%, respectively. Also, treatments of 5 with n-butyl, tert-butyl, and cyclohexyl isocyanides result in its insertion into both of the Pd-C bonds to form iminoacyl Pd complexes trans,trans-(Me₃P)₂IPd-C(=N-R)C₄H ₂SC(=N-R)-PdI(PMe₃)₂ (R=n-Bu, 12; t-Bu, 13; cyclohexyl, 14), respectively.

Full text of DOI:10.1016/S0022-328X(99)00391-5

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 588 (1999) 268–277
Synthesis and reactions of mono- and dipalladium complexes
containing 2-thienyl and 2,5 (or 2,5%) -bridged thienylene (or
dithienylene) ligand: new dipalladium complex formation
connected by thioketene part via CꢀS bond cleavage of thiophene
Yong-Joo Kim a,*, Sang-Chul Lee a, Moon Hwan Cho b, Soon-W. Lee c
a Department of Chemistry, Kangnung National Uni6ersity, Kangnung 210-702, South Korea
b Department of Chemistry, Kangwon National Uni6ersity, Chuncheon 200-701, South Korea
c Department of Chemistry, Sung Kyun Kwan Uni6ersity, Suwon 440-746, South Korea
Received 20 April 1999; received in revised form 29 June 1999
Abstract
Oxidative addition reactions of 2-iodothiophene, 2-bromothiophene, and 2,5-dibromothiophene with equimolar
Pd(CH2ꢁCHPh)L2 (L=PMe3 and PEt3) at room temperature in THF produce mononuclear s-thienyl palladium(II) complexes
trans-(2-C4H3S)PdX(PMe3)2 (X=I, 1; X=Br, 2) and trans-(5-Br(2-C4H2S))PdBrL2 (L=PMe3, 3; L=PEt3, 4). Reactions using
2,5-dibromothiophene, 2,5-diiodothiophene, and 5,5-dibromo-2,2%-bithiophene under 2:1 molar ratio in THF give thienylene (or
dithienylene) bridged dipalladium complexes trans,trans-L2XPd(m-2,5-C4H2S)PdXL2 (L=PMe3; X=I, 5; Br, 6; L=PEt3; X=Br,
7) and trans,trans-(Me3P)2BrPd(m-2,5%-C4H2S-C4H2S)PdBr(PMe3)2 (8), in high yields. However, the equimolar reaction of
2,5-dibromothiophene with the Pd(0) complex results in formation of
a
dinuclear complex cis,trans-[(Me3P)2Pd(h2-
SꢁCꢁCHꢀCHꢁCBr)PdBr(PMe3)2 (9), in 56% yield via CꢀS bond cleavage of the thiophene ring. All the complexes provided
satisfactory IR and NMR (1H, 31P{1H}, and 13C{1H}) spectra as well as elemental analyses. Molecular structures of 1, 7, and 9
were confirmed by X-ray crystallography. Treatment of 5 and 7 with CO (1 atm) results in CO insertion into one of the PdꢀC
bonds to give trans,trans-(Me3P)2IPdC(O)C4H2SPdI(PMe3)2 (10) in 94% and trans,trans-(Et3P)2BrPdC(O)C4H2SPdBr(PEt3)2 (11)
in 23%, respectively. Also, treatments of 5 with n-butyl, tert-butyl, and cyclohexyl isocyanides result in its insertion into both of
the PdꢀC bonds to form iminoacyl Pd complexes trans,trans-(Me3P)2IPdꢀC(ꢁNꢀR)C4H2SC(ꢁNꢀR)ꢀPdI(PMe3)2 (R=n-Bu, 12;
t-Bu, 13; cyclohexyl, 14), respectively. © 1999 Elsevier Science S.A. All rights reserved.
Keywords: Palladium; Thienyl; Thienylene bridged; Dipalladium complex; Thioketene
bis(trimethylstannyl)thiophene [1], thienylmercury chlo-
ride [5], and thienyllithium compounds [1,6] and also
1. Introduction
from the oxidative addition reactions of halothiophene
compounds with Pd(PPh3)4 [2,5,7]. In particular, the
oxidative addition of dihalothiophenes to zerovalent
complexes of Group 10 metals is expected to provide a
convenient synthetic route to the dinuclear metal com-
plexes with a bridging thienylene ligand. We have re-
cently synthesized a series of bridging arylene or
diarylene dinickel(II) and dipalladium(II) complexes [8]
by the oxidative addition reactions of dihaloarene with
Ni(0) and Pd(0) compounds. The produced complexes
possess a unique structure containing the p-conjugated
ligand between two metal centers and show unique
Thienyl group bonded Group 10 metal complexes
have been studied as a model for elucidation of the
dp–pp interactions between transition metal and p-con-
jugated groups and as the catalytic intermediates for
regioselective reduction and/or for conducting polymer-
ization using these metals [1–3]. Several thienyl or
thienylene bridged complexes of these metals were pre-
pared from the reactions of metal halide complexes
with
2-trimethylstannylthiophene
[4]
or
2,5-
* Corresponding author. Fax: +82-391-6471183.
E-mail address: yjkim@knusun.kangnung.ac.kr (Y.-J. Kim)
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00391-5

Y.-J. Kim et al. / Journal of Organometallic Chemistry 588 (1999) 268–277
269
chemical properties such as the insertion of small
molecules into the metalꢀcarbon bond. This allows us
to study the structure and chemical properties of other
electron delocalized compounds such as thiophenes.
In this work we have focused on the preparation of
Reaction of 3 with equimolar Pd(CH2ꢁCHPh)-
(PMe3)2 also causes the formation of dinuclear complex
6, suggesting the stepwise oxidative addition of the two
CꢀBr bonds in the substrate to the Pd(0) centers.
Previously, we observed similar results on the pathway
of diarylene bridged dinuclear Pd complex formation
[8b].
The trans configuration around the Pd centers in the
above complexes (1–8) is supported by the 1H- and
13C-NMR signals of PMe3 or PEt3 ligands showing
apparent triplets (PꢀCH3) or quintet (CH3 of PEt3)
arising from virtual coupling [10]. The 31P{1H}-NMR
spectra of 1–8 show a singlet in agreement with a trans
configuration having two or four magnetically equiva-
lent PR3 ligands. Fig. 1 shows the molecular structure
of 1 with the atomic numbering scheme determined by
X-ray crystallography. Selected bond lengths and an-
gles of the complex are listed in Table 1. The coordina-
tion sphere of the Pd metal in 1 can be described as a
slightly distorted square plane. The molecular plane,
defined by Pd, P(1), P(2), I, and C(1), is with the
dinuclear palladium complexes with
a
bridging
thienylene and dithienylene ligand including thienyl
monopalladium complexes via oxidative addition of
dihalothiophene and dihalobithiophene compounds and
their reaction with isocyanides and CO to result in their
insertion into PdꢀC bonds.
2. Results and discussion
2.1. Preparation and structure of thienyl palladium(II)
or bridging thienylene dipalladium(II) complexes
Reactions of Pd(CH2ꢁCHPh)L2 (L=PMe3, PEt3) [9],
which are generated in situ from the reaction of trans-
PdEt2L2 with styrene, with equimolar 2-iodothiophene,
2-bromothiophene, and 2,5-dibromothiophene in THF
at room temperature give mononuclear s-thienyl palla-
dium(II) complexes (2-C4H3S)PdX(PMe3)2 (X=I, 1;
Br, 2) and 5-Br(2-C4H2S)PdBrL2 (L=PMe3 (3), PEt3
(4) in high yields, respectively, as shown in Eq. (1).
These reactions can also be carried out in a hexane
media.
,
average atomic displacement of 0.001 A. The thienyl
ring is also nearly planar with the average atomic
,
displacement of 0.006 A and is almost perpendicular to
the molecular plane with a dihedral angle 85.9(1)°. Fig.
2 shows an expected dinuclear form of 7. There are two
crystallographically independent molecules in the asym-
metric unit. The two molecules are chemically equiva-
lent and almost perpendicular to each other, the
dihedral angle between the two thiophene rings is
87.7(2)8°. The coordination sphere of each Pd can be
described as a square plane. The equatorial planes
(Pd(1), Br(1), P(1), P(2), C(13)and Pd(2), Br(2), P(3),
P(4), C(16)) are nearly planar with the atomic displace-
,
ment not exceeding 0.0665 A. The thiophene ring (S(1),
C(13), C(14), C(15), and C(16)) is essentially planar
(1)
,
Similar reactions of 2,5-dibromothiophene, 2,5-di-
iodothiophene, and 5,5%-dibromo-2,2%-bithiophene with
Pd(CH2ꢁCHPh)L2 in a 1:2 molar ratio in THF or
toluene lead to oxidative addition of CꢀX bonds to two
Pd centers giving dinuclear palladium complexes with
bridging thienylene or dithienylene ligand, L2XPd(m-
2,5-C4H2Sꢀ)PdXL2 (L=PMe3; X=I, 5; Br, 6; L=
PEt3; X=Br, 7) and trans,trans-(Me3P)2BrPd(m-
2,5%-C4H2SꢀC4H2S)PdBr(PMe3)2 (8), in moderately
good yields, respectively, as shown in Eq. (2).
with the average atomic displacement of 0.0070 A and
this ring is almost perpendicular to the two equatorial
planes with the dihedral angles of 86.0(2)° and 81.4(2)°.
Fig. 1. ORTEP drawing of 1 showing the atomic labeling scheme and
50% probability thermal ellipsoids.
(2)

270
Y.-J. Kim et al. / Journal of Organometallic Chemistry 588 (1999) 268–277
Table 1
a
,
Selected bond lengths (A) and angles (°) for 1 and 7
Complex 1
PdꢀC(1)
PdꢀP(1)
PdꢀP(2)
PdꢀI
2.015(6)
2.314(2)
2.324(2)
2.6667(9) C(1)ꢀPdꢀI
1.582(10) C(4)ꢀSꢀC(1)
C(1)ꢀPdꢀP(1)
C(1)ꢀPdꢀP(2)
P(1)ꢀPdꢀP(2)
88.5(2)
87.4(2)
175.86(5)
179.7(2)
96.9(4)
SꢀC(4)
SꢀC(1)
1.622(7)
1.589(5)
1.575(7)
1.328(14) C(3)ꢀC(2)ꢀC(1)
C(4)ꢀC(3)ꢀC(2)
C(2)ꢀC(1)ꢀS
C(2)ꢀC(1)ꢀPd
SꢀC(1)ꢀPd
114.0(4)
123.6(4)
122.4(3)
97.9(4)
115.7(6)
115.5(6)
C(1)ꢀC(2)
C(2)ꢀC(3)
C(3)ꢀC(4)
C(3)ꢀC(4)ꢀS
Complex 7
Pd(1)ꢀC(13)
Pd(1)ꢀP(2)
Fig. 2. ORTEP drawing of 7 showing the atomic labeling scheme and
50% probability thermal ellipsoids. One of the two crystallographi-
cally independent molecules is shown.
2.012(8)
2.310(2)
2.319(2)
Pd(3)ꢀC(41)
Pd(3)ꢀP(6)
Pd(3)ꢀP(5)
2.006(9)
2.313(3)
2.312(2)
2.4939(12)
2.002(8)
2.319(3)
2.323(3)
2.5013(12)
1.725(8)
1.723(8)
1.381(12)
1.430(12)
1.354(12)
88.8(2)
Pd(1)ꢀP(1)
Pd(1)ꢀBr(1)
Pd(2)ꢀC(16)
Pd(2)ꢀP(4)
Pd(2)ꢀP(3)
Pd(2)ꢀBr(2)
S(1)ꢀC(16)
2.4922(11) Pd(3)ꢀBr(3)
Fig. 3 shows the molecular structure of 9 confirmed
by X-ray crystallography. The ORTEP drawing displays
that one Pd(1) atom containing two mutually trans
PMe3 ligands and Br is coordinated to C(4) of bridging
SꢁCꢁCHꢀCHꢁCBr and the other Pd(2) atom contain-
ing two mutually cis PMe3 ligand is coordinated in an
h2-C,S fashion to the thioketene part of
SꢁCꢁCHꢀCHꢁCBr connecting two Pd centers. Two
square planar planes are almost perpendicular with a
dihedral angle of 88.70(9)°. The bond lengths of
2.017(8)
2.311(3)
2.325(2)
2.4951(12) Pd(4)ꢀBr(4)
1.737(8)
1.738(8)
1.339(12) C(41)ꢀC(42)
1.441(11) C(42)ꢀC(43)
1.333(12) C(43)ꢀC(44)
89.8(2)
87.6(2)
Pd(4)ꢀC(44)
Pd(4)ꢀP(7)
Pd(4)ꢀP(8)
S(2)ꢀC(44)
S(2)ꢀC(41)
S(1)ꢀC(13)
C(13)ꢀC(14)
C(14)ꢀC(15)
C(15)ꢀC(16)
C(13)ꢀPd(1)ꢀP(2)
C(13)ꢀPd(1)ꢀP(1)
P(2)ꢀPd(1)ꢀP(1)
C(41)ꢀPd(3)ꢀP(6)
C(41)ꢀPd(3)ꢀP(5)
P(6)ꢀPd(3)ꢀP(5)
86.9(2)
174.23(9)
175.66(9)
,
,
C(1)ꢀC(2) (1.310 A) and C(3)ꢀC(4) (1.329 A) (Table 2)
C(13)ꢀPd(1)ꢀBr(1) 177.5(2)
C(41)ꢀPd(3)ꢀBr(3) 179.1(2)
are near to the bond length of normal double bonds
P(2)ꢀPd(1)ꢀBr(1)
C(16)ꢀPd(2)ꢀP(4)
C(16)ꢀPd(2)ꢀP(3)
P(4)ꢀPd(2)ꢀP(3)
C(16)ꢀPd(2)ꢀBr(2) 179.3(3)
P(3)ꢀPd(2)ꢀBr(2)
C(16)ꢀS(1)ꢀC(13)
C(14)ꢀC(13)ꢀS(1) 107.9(6)
C(14)ꢀC(13)ꢀPd(1) 131.3(6)
S(1)ꢀC(13)ꢀPd(1) 120.7(5)
87.85(7)
89.2(2)
88.2(2)
P(6)ꢀPd(3)ꢀBr(3)
C(44)ꢀPd(4)ꢀP(7)
C(44)ꢀPd(4)ꢀP(8)
P(7)ꢀPd(4)ꢀP(8)
C(44)ꢀPd(4)ꢀBr(4) 176.3(2)
P(7)ꢀPd(4)ꢀBr(4)
C(41)ꢀS(2)ꢀC(44)
C(42)ꢀC(41)ꢀS(2) 108.3(6)
C(42)ꢀC(41)ꢀPd(3) 128.5(6)
S(2)ꢀC(41)ꢀPd(3) 123.1(5)
90.63(8)
87.5(2)
89.4(2)
,
(1.33A) but are slightly shorter than those
,
,
(C(13)ꢀC(14), 1.34 A and C(15)ꢀC(16), 1.33 A) of
173.57(10)
170.66(10)
bridged thienyl ring of 7. The C(1)ꢀS(1) bond length
,
(1.698 A) is close to the CꢀS bond lengths previously
91.98(7)
94.3(4)
93.86(7)
95.7(4)
reported for C5H5Co(h2ꢀSꢁCꢁCCMe2[CH2]3CMe2)-
2
i
,
PMe3 (1.695(7) A) [11a], C5H5Rh(h -SꢁCꢁCH2)(PPr3)
(1.69(3) A) [11b], and [CpRu(dppm)(h2-SꢁCꢁ
,
,
CHPh]PF6 (CꢀS; 1.671(4) A) [12]. Most of the already
reported thioketene complexes were obtained by
a Symmetry transformations used to generate equivalent atoms.
ligand exchange with
a stable thioketene or by
the addition of elemental sulfur to a vinylidene com-
plex [11,13,14]. Complex 9 is the first example of for-
In addition, the two equatorial planes are twisted with
the dihedral angle of 35.2(1)°.
mation of the Pd complex containing
a
co-
Reaction of Pd(CH2ꢁCHPh)(PMe3)2 with an equimo-
lar amount of 2,5-dibromothiophene in THF at room
temperature gives
a dinuclear complex cis,trans-
(Me3P)2Pd(h2-SꢁCꢁCHꢀCHꢁCBr)PdBr(PMe3)2 (9), in
56% yield, which is formed via cleavage of the CꢀS
bond in thiophene ring as shown in Eq. (3).
Fig. 3. ORTEP drawing of 9 showing the atomic labeling scheme and
50% probability thermal ellipsoids.
(3)

Y.-J. Kim et al. / Journal of Organometallic Chemistry 588 (1999) 268–277
271
Table 2
Selected bond lengths (A) and angles (°) for 9
to thermal decomposition of 9 in solution at room
temperature. These reactions are monitored by H- and
,
1
31P-NMR. It is also observed that isolated 9 is ther-
mally unstable at room temperature in solution and
changes slowly into the unidentified species. The reac-
tion (Eq. (3)) occurs exclusively in the presence of an
equimolar or excess amounts of 2,5-dibromothiophene
although the detailed mechanism of CꢀS bond cleavage
in the thiophene ring is not clear at present. As one of
the possible pathways, oxidative addition of 2,5-dibro-
mothiophene to Pd(0) complex might occur to give 3.
The complex was then rearranged to give the intermedi-
ate containing thiokene group, (SꢁCꢁCHꢀCHꢁCBr)-
PdBr(PMe3)2 via CꢀS bond cleavage of the thiophene
ring whose thioketene part is coordinated in an h2-C,S
fashion to the other Pd(0) complex.
In order to obtain insight into the pathway of the
reaction, we have examined the reaction of 3 with Pd(0)
complex Pd(CH2ꢁCHPh)(PMe3)2. The reaction in THF
or toluene in 1:1 molar ratio affords a thienylene
bridged dipalladium complex 6 as a grayish white solid
as well as unidentified species as a minor product,
whereas the reaction in the presence of 2,5-dibromo-
thiophene similarly to Eq. (3) causes formation of 3 as
sole product. These results do not provide any clue to
elucidate detailed mechanism of CꢀS bond cleavage of
thiophene ring.
,
Bond lengths (A)
Pd(1)ꢀC(4)
Pd(1)ꢀP(2)
Pd(2)ꢀC(1)
Pd(2)ꢀS(1)
Br(2)ꢀC(4)
C(1)ꢀC(2)
C(3)ꢀC(4)
1.977(9)
2.306(3)
2.051(10) Pd(2)ꢀP(3)
2.317(3)
1.929(9)
Pd(1)ꢀP(1)
Pd(1)ꢀBr(1)
2.297(3)
2.5012(14)
2.276(3)
2.336(3)
1.698(10)
1.462(13)
Pd(2)ꢀP(4)
S(1)ꢀC(1)
1.310(12) C(2)ꢀC(3)
1.329(13)
Bond angles (°)
C(4)ꢀPd(1)ꢀP(1)
P(1)ꢀPd(1)ꢀP(2)
P(1)ꢀPd(1)ꢀBr(1)
C(1)ꢀPd(2)ꢀP(3)
P(3)ꢀPd(2)ꢀS(1)
P(3)ꢀPd(2)ꢀP(4)
C(1)ꢀS(1)ꢀPd(2)
C(2)ꢀC(1)ꢀPd(2)
C(1)ꢀC(2)ꢀC(3)
C(3)ꢀC(4)ꢀBr(2)
89.6(3)
175.39(10)
90.33(8)
106.4(3)
151.57(11)
102.39(11)
59.1(3)
146.1(8)
122.9(9)
115.5(7)
C(4)ꢀPd(1)ꢀP(2)
C(4)ꢀPd(1)ꢀBr(1) 176.6(3)
P(2)ꢀPd(1)ꢀBr(1)
C(1)ꢀPd(2)ꢀS(1)
C(1)ꢀPd(2)ꢀP(4)
S(1)ꢀPd(2)ꢀP(4)
90.0(3)
90.40(8)
45.2(3)
151.1(3)
106.04(10)
C(33)ꢀP(3)ꢀPd(2) 113.7(4)
S(1)ꢀC(1)ꢀPd(2)
C(4)ꢀC(3)ꢀC(2)
C(3)ꢀC(4)ꢀPd(1)
75.7(4)
125.0(9)
132.7(7)
Br(2)ꢀC(4)ꢀPd(1) 111.9(5)
ordinated thioketene ligand via CꢀS bond cleavage in
the thiophene ring under mild conditions. Related CꢀS
bond cleavage of thiophene or thiophene derivatives
using metal complexes in low oxidation states including
the Pt(0) complex have been reported [15–20]. The
1H-NMR spectrum of the unsymmetrical dinuclear Pd
complex 9 shows an apparent triplet at 1.32 ppm due to
virtual coupling of PMe3 ligands coordinated to the
square-planar Pd center and two set of doublets at 0.90,
1.08 ppm due to two unequivalent PMe3 ligands
bonded to the three-coordinated Pd center. A singlet at
l −15.6 and two sets of doublets at l −17.0 and
−26.8 (J=14.6 Hz) at −30°C in the 31P{1H}-spec-
2.2. Reactions of CO and isocyanide with bridging
thienylene dipalladium complexes
Treatment of 5 and 7 with CO (1 atm) at room
temperature causes smooth CO insertion to give
trans,trans-[L2XPdC(O)C4H2SPdXL2] (L=PMe3 X=I
(10) L=PEt3 X=Br (11) in 99 and 23% yields as
shown in Eq. (4), respectively.
1
trum also support these configurations. The H-NMR
signals of the bridging ligand are observed at l 6.47 and
7.61. The former signal showing splitting due to PꢀH
coupling (14 Hz) is assigned to SꢁCꢁCHꢀ hydrogen. A
larger J(HH) value of the signals (10 Hz) than the two
3, 4 hydrogens of the common thiophene ring (J=3–5
Hz) [16c, 21] indicates the s-trans structure of the
1,3-diene unit. These signals are evidently different
from those of thienylene bridged dinuclear complexes
5–7 having a singlet at l 6.51–6.86. The 13C{1H}-
NMR signals of the SꢁCꢁCHꢀCHꢁCBr group are ob-
served at l 106.4, 128.3, 131.2, and 141.7.
The reaction (Eq. (3)) is dependent on solvent and on
the substrate to complex molar ratio. The same reac-
tion in hexane produces a 2-thienyl complex 3, which is
separated from the solution due to its low solubility in
hexane. However, the reaction in THF in a 2:1 molar
ratio gives a mixture of 9 and thienylene bridged dinu-
clear complex 6 after 30 min stirring. On further stir-
ring the reaction mixture changes into a mixture of 9, 6,
and an unidentified species that may be produced due
(4)
Complex 11 has quite a similar solubility to the
starting material and was not isolated by fractional
crystallization. Also, the lower yield of 11 than 10 may
be due to a larger steric hindrance of PEt3 than PMe3
for CO insertion into a PdꢀC bond in the thienylene
bridged complex. The reaction occurs selectively at one
of the PdꢀC bonds and shows no further CO insertion.
Previously, we also observed similar selective CO inser-
tion into a PdꢀC bond of arylene or biarylene bridged
dinuclear Pd complexes [8b].
IR spectra show a strong w(CO) absorption at 1598
cm−1. The 13C-NMR signals at l 220–222 support the

272
Y.-J. Kim et al. / Journal of Organometallic Chemistry 588 (1999) 268–277
single CO insertion into PdꢀC bond of the thienylene
dipalladium complexes during the reaction. Two triplets
for PMe3 ligand (10) and two triplets and two singlets
for PEt3 (11) in the 13C-NMR spectra as well as two
singlets in the 31P{1H}-NMR spectra support the pres-
ence of inequivalent phosphine ligands due to the un-
symmetrical molecular structure.
3. Experimental
3.1. General, materials, and measurement
All manipulations of air-sensitive compounds were
performed under N2 or argon atmosphere with use of
standard Schlenk technique. Solvents were distilled
from Naꢀbenzophenone. PMe3, PEt3, and halothio-
phenes were purchased from Aldrich and used without
further purification. 5,5%-Dibromo-2,2%-thiophene was
prepared by the literature method [24]. trans-PdEt2L2
(L=PMe3, PEt3) [9] were prepared by the literature
methods.
Elemental analyses were carried out by the analytical
laboratory, Basic Science Institute of Korea and Sangji
University. UV–vis and IR spectra were recorded on a
Hitachi 200-20 and 270-30 spectrophotometer, respec-
tively. NMR (1H, 13C{1H} and 31P{1H}) spectra were
obtained on Jeol-Lamda-300, 400 MHz and Bruker 300
MHz spectrometers. Chemical shifts were referred to
internal Me4Si or to external 85% H3PO4.
Reaction of 5 with two times molar butyl isocyanide
at room temperature gives a complex with the symmet-
rical
structure
trans,trans-(Me3P)2IPdꢀC(ꢁN-n-
Bu)C4H2SC(ꢁN-n-Bu)ꢀPdI(PMe3)2 (12) in 69% yield.
The IR spectrum shows a strong absorption band at
1574 cm−1, which can be assigned to w(CꢁN) for the
iminoacyl metal complex [1b, 22]. The crude product
before purification shows an absorption band at 2160
cm−1 assigned to w(CꢂN) of the isonitrile coordinated
to a Pd centre. These results suggest that the reaction
gives not only 12 but also cationic complexes such
as
[(Me3P)2(CNꢀR)PdꢀC4H2SꢀPd(CNꢀR)(PMe3)2]I2
or [(Me3P)2IPdꢀC(ꢁNꢀR)C4H2SꢀPd(CNꢀR)(PMe3)2]I
(R=nꢀBu) which may be regarded as the intermediate
for formation of 12. Other reactions with more bulky
isocyanides such as tert-butyl or cyclohexyl isocyanides
also gave the cationic adducts and the neutral com-
plexes with the symmetrical structure trans,trans-
(Me3P)2IPdꢀC(ꢁNꢀR)C4H2SC(ꢁNꢀR)ꢀPdI(PMe3)2 (R=
t-Bu, 13 and cyclohexyl, 14). Complexes 13 and
14 were isolated by repeated recrystallization in the
yields of 49 and 60% respectively. Previously, Sono-
gashira and co-workers [1b] have reported that inser-
tion of aryl isocyanide into the PtꢀC bonds of thienyl
bridged diplatinum complexes occurs to give the un-
symmetric or symmetric iminodiplatinum complexes at
much higher temperature and their insertion is affected
by the bulkiness of isocyanide and ligands on platinum.
In our case using less bulky or bulky isocyanides,
iminoacyl palladium complexes with symmetrical struc-
ture are easily formed under mild conditions. These
results indicate that isocyanide insertion into the PdꢀC
bonds of thienylene bridged dipalladium complexes oc-
curs more easily, than into the PtꢀC bonds of
thienylene bridged diplatinum complexes. Previous
work by Mantovani et al. [23] also showed that iso-
cyanide insertion at room temperature occurs in the
PdꢀC bond of 2-thienylpalladium complex.
3.2. Preparation of thienyl palladium(II) complexes
trans-[(2-C4H3S)PdX(PMe3)2], (X=I, 1; Br, 2),
trans-[(2-(5-BrC4H2S)PdBr(PMe3)2] (3), and
trans-[(2-(5-BrC4H2S)PdBr(PEt3)2] (4)
To a Schlenk flask containing trans-PdEt2(PMe3)2
(0.413 g, 1.31 mmol) at 0°C were added styrene (0.544
g, 5.24 mmol) and THF (4 ml) in that order. The
mixture was heated at 55°C for 3 h to give a pale yellow
solution. At 0°C 2-iodothiophene (0.274 g, 1.31 mmol)
was added to the solution. After stirring of the mixture
for 2 h at room temperature (r.t.), the solvent was
evaporated to ca. 2 ml under reduced pressure. Addi-
tion of Et2O and storage at −30°C resulted in a white
solid which was filtered off, washed with hexane and
then with Et2O and recrystallized from THF–hexane to
give trans-[(2-C4H3S)PdI(PMe3)2] (1) as slightly gray
crystals (0.577 g, 95%). UV–vis (umax nm): 302 (m 3800),
1
250 (m 14700). H-NMR (300 MHz, CDCl3, l); 1.03 (t,
J=3.6 Hz, 18H, PMe3), 6.62 (d, J=3.4 Hz, 1H,
thienyl), 7.07 (dd, J=3.3, 5.0 Hz, 1H, thienyl), 7.42
(dd, J=4.3, 0.8 Hz, 1H, thienyl). 13C{1H}-NMR (75
MHz, CDCl3, l); 15.7 (t, J(CP)=15.8 Hz, PMe3),
127.2 (t, J(CP)=2.6 Hz, thienyl), 127.3 (s, thienyl),
128.2 (t, J(CP)=4.6 Hz, thienyl), 146.5 (t, J(CP)=9.3
Hz, thienyl). 31P{1H}-NMR (120 MHz, CDCl3, l);
−17.3 (s). Anal. Calc. for C10H21SIP2Pd: C, 25.63; H,
4.52; S, 6.84. Found: C, 25.45; H, 4.29; S, 6.86.
trans-[(2-C4H3S)PdBr(PMe3)2] (2), trans-[(2-(5-BrC4-
H2S)PdBr(PMe3)2] (3), and trans-[(2-(5-BrC4H2S)-
PdBr(PEt3)2] (4) were obtained similarly in 95, 98, and
85% yields, respectively.
In summary, we prepared thienyl palladium(II) and
thienylene (or dithienylene) bridged dipalladium com-
plexes from the oxidative addition of halothiophenes or
dihalothiophenes with Pd(CH2ꢁCHPh)L2 (L=PMe3 or
PEt3). Also, we have observed unusual CꢀS bond cleav-
age of thiophene ring to give a dipalladium complex
connected by the thioketene part in the oxidative addi-
tion using equimolar or excess amounts of 2,5-di-
bromothiophene. The thienylene bridged dipalladium
complexes undergo insertion of small molecules such as
CO and isocyanide into their PdꢀC bond at room
temperature.
Complex 2: UV–vis(umax nm): 298 (m 9800), 250 (m
37600).1H-NMR (300 MHz, CDCl3, l); 1.26 (t, J=3.6

Y.-J. Kim et al. / Journal of Organometallic Chemistry 588 (1999) 268–277
273
Hz, 18H, PMe3), 6.62 (d, J=3.4 Hz, thienyl), 7.05 (dd,
J=3.3, 5.0 Hz, 1H, thienyl), 7.40 (dd, J=5.0, 0.8 Hz,
1H, thienyl). 13C{1H}-NMR (75 MHz, CDCl3, l); 14.0
(t, J(CP)=15.9 Hz, PMe3), 127.1 (t, J(CP)=2.8 Hz,
thienyl), 127.2 (s, thienyl), 128.2 (t, J(CP)=4.7 Hz,
thienyl), 143.1 (t, J(CP)=10 Hz, thienyl). 31P{1H}-
NMR (120 MHz, CDCl3, l); −20.6 (s). Anal. Calc. for
C10H21SBrP2Pd: C, 28.49; H, 5.02; S, 7.61. Found: C,
28.62; H, 4.92; S, 7.73.
trans,trans-[(Me3P)2BrPd(m-2,5-C4H2S)PdBr(PMe3)2]
(6), trans,trans-[(Et3P)2BrPd(m-2,5-C4H2S)PdBr(PEt3)2]
(7), and trans,trans-[(Me3P)2BrPd(m-2,5%-C4H2S-C4H2-
S)PdBr(PMe3)2] (8) were similarly obtained in 75, 80,
and 98% yields, respectively.
Complex 6: UV–vis (umax nm): 275 (m 11400).1H-
NMR (300 MHz, CDCl3, l); 1.29 (t, J=3.6 Hz, 36H,
PMe3), 6.60 (s, 2H, thienylene). 13C{1H}-NMR (75
MHz, CDCl3, l); 14.4 (t, J(CP)=15.8 Hz, PMe3),
129.9 (t, J(CP)=4.6 Hz, thienylene), 142.1 (t, J(CP)=
10.1 Hz, thienylene). 31P{1H}-NMR (120 MHz, CDCl3,
l); −18.2 (s). Anal. Calc. for C16H38SBr2P4Pd2: C,
25.32; H, 5.05; S, 4.22. Found: C, 25.40; H, 5.11; S,
4.24.
1
Complex 3: H-NMR (300 MHz, CDCl3, l); 0.86 (t,
J=3.5 Hz, 18H, PMe3), 6.36 (d, J=3.0 Hz, thienyl),
7.00 (dd, J=3.6 Hz, 1H, thienyl). 13C{1H}-NMR (75
MHz, CDCl3, l); 13.7 (t, J(CP)=15.4 Hz, PMe3),
111.0 (t, J(CP)=3.0 Hz, thienyl), 129.7 (t, J(CP)=4.5
Hz, thienyl), 130.9 (s, thienyl) 148.3 (t, J(CP)=11 Hz,
thienyl). 31P{1H}-NMR (120 MHz, CDCl3, l); −16.0
(s). Anal. Calc. for C10H20SBr2P2Pd: C, 24.00; H, 4.03;
S, 6.41. Found: C, 24.04; H, 4.10; S, 6.47.
Complex 7: 1H-NMR (300 MHz, CDCl3, l); 1.11
(apparent quintet, 36H, P(CH2CH3)3), 1.67 (m, 24H,
P(CH2CH3)3) 6.51 (s, 2H, thienylene). 13C{1H}-NMR
(75 MHz, CDCl3, l); 8.1 (s, P(CH2CH3)3), 14.2 (t,
J(CP)=13.7 Hz, P(CH2CH3)3), 129.6 (s, thienylene),
143.8 (t, J(CP)=10.2 Hz, thienylene). 31P{1H}-NMR
(120 MHz, CDCl3, l); 12.8 (s). Anal. Calc. for
C28H62SBr2P4Pd2: C, 36.26; H, 6.74; S, 3.46. Found: C,
36.27; H, 6.76; S, 3.43.
Complex 8: UV–vis(umax nm): 346 (m 26 400), 275 (m
20 000).1H-NMR (300 MHz, CDCl3, l); 1.32 (t, J=3.5
Hz, 36H, PMe3), 6.46 (d, J=3.6 Hz, 2H, thienylene),
6.97 (d, J=3.3 Hz, 2H, thienylene). 13C{1H}-NMR (75
MHz, CDCl3, l); 14.2 (t, J(CP)=15.1 Hz, PMe3),
122.6 (s, thienylene), 129.2 (t, J(CP)=4.6 Hz,
thienylene), 141.0 (s, thienylene), 142.0 (t, J(CP)=10.5
Hz, thienylene). 31P{1H}-NMR (120 MHz, CDCl3, l);
−21.6 (s). Anal. Calc. for C20H40S2Br2P4Pd2: C, 28.56;
H, 4.79; S, 7.62. Found: C, 28.72; H, 4.97; S, 7.70.
Complex 4: 1H-NMR (300 MHz, CDCl3, l); 1.10
(apparent quintet, 18H, P(CH2CH3)3), 1.68 (m, 12H,
P(CH2CH3)3), 6.36 (d, J=3.5 Hz, 1H, thienyl), 6.91 (d,
J=3.4 Hz, 1H, thienyl). 13C{1H}-NMR (75 MHz,
CDCl3, l); 8.2 (s, P(CH2CH3)3)), 14.5 (t, J(CP)=13.6
Hz, P(CH2CH3)3) 110.7 (s, thienyl), 130.0 (t, J(CP)=
3.8 Hz, thienyl), 130.2 (s, thienyl) 145.7 (t, J(CP)=10
Hz, thienyl). 31P{1H}-NMR (120 MHz, CDCl3, l); 15.3
(s). Anal. Calc. for C16H32SBr2P2Pd: C, 32.87; H, 5.52;
S, 5.48. Found: C, 32.92; H, 5.96; S, 5.84.
3.3. Preparation of bridging thienylene(or dithienylene)
dipalladium complexes trans,trans-[(Me3P)2XPd(v-
2,5-C4H2S)PdX(PMe3)2] (X=I (5); Br (6)), trans,
trans-[(Et3P)2BrPd(v-2,5-C4H2S)PdBr(PEt3)2] (7), and
trans,trans-[(Me3P)2BrPd(v-2,5%-C4H2SꢀC4H2S)-
PdBr(PMe3)2] (8)
To a Schlenk flask containing trans-PdEt2(PMe3)2
(0.577 g, 1.82 mmol) at 0°C were added styrene (0.759
g, 7.36 mmol) and THF (4 ml) in this order. The
mixture was heated at 55°C for 3 h to give a pale yellow
solution. At 0°C 2,5-diiododothiophene (0.300 g, 0.89
mmol) was added to the mixture. After stirring the
mixture for 3 h at r.t. the solvent was evaporated to ca.
2 ml under reduced pressure. Addition of Et2O (2 ml)
and storage at −30°C in a freezer resulted in a pale
yellow solid which was filtered off, washed with hexane
and then with Et2O and recrystallized from THF–Et2O
to give as pale yellow crystals of trans,trans-
[(Me3P)2IPd(m-2,5-C4H2S)PdI(PMe3)2] (5) (0.694 g,
91%). UV–vis(umax nm): 316 (m 7600), 274 (m 19600).1H-
NMR (300 MHz, CDCl3, l); 1.38 (t, J=3.4 Hz, 36H,
PMe3), 6.63 (s, 2H, thienylene). 13C{1H}-NMR (75
MHz, CDCl3, l); 16.1 (t, J(CP)=16.0 Hz, PMe3),
129.9 (t, J(CP)=4.6 Hz, thienylene), 145.0 (s,
thienylene). 31P{1H}-NMR (120 MHz, CDCl3, l); −
20.8 (s). Anal. Calc. for C16H38SI2P4Pd2: C, 22.50; H,
4.48; S, 6.41. Found: C, 22.62; H, 4.50; S, 6.39.
3.4. Preparation of cis,trans-[(Meꢀ3P)2Pd(p2-
SꢁCꢁCHꢀCHꢁCBr)PdBr(PMe3)2 (9)
To a Schlenk flask containing trans-PdEt2(PMe3)2
(0.210 g, 0.662 mmol) at 0°C were added styrene (0.276
g, 2.65 mmol) and THF (2 ml) in this order. The
mixture was heated at 55°C for 3 h to give a pale yellow
solution. At 0°C 2,5-dibromothiophene (0.160 g, 0.662
mmol) was added to the solution. After stirring the
mixture for 3 h at r.t. the solvent was evaporated to 1
ml under reduced pressure. Addition of Et2O (3 ml) and
storage at −30°C resulted in a pale yellow solid which
was filtered off, washed with hexane (2×2 ml) and
recrystallized from THF–hexane (3:1) to give as yellow
crystals of cis,trans-[(Meꢀ3P)-2Pd(h2-SꢁCꢁCHꢀCHꢁ
CBr)PdBr(PMe3)2 (9) (0.140 g, 56%). 1H-NMR (300
MHz, C6D6, l); 0.90 d, J=8.2 Hz, 9H, cis PMe3). 1.08
(d, J=8.2 Hz, 9H, cis PMe3), 1.32 (t, J=3.6 Hz, 18H,
trans PMe3), 6.47 (dd, J=9.6, 13.7 Hz, 1H,
SꢁCꢁCHꢀCHꢁCBr),
7.61(d,
J=9.6
Hz,
1H,
SꢁCꢁCHꢀCHꢁCBr). 13C{1H}-NMR (75 MHz, C6D6,

274
Y.-J. Kim et al. / Journal of Organometallic Chemistry 588 (1999) 268–277
l); 14.6 (t, J(CP)=14.8 Hz, PMe3), 18.0 (apparent
triplet, PMe3), 106.4 (s, SꢁCꢁCHꢀCHꢁCBr), 128.3 (s,
SꢁCꢁCHꢀCHꢁCBr), 131.2 (s, SꢁCꢁCHꢀCHꢁCBr),
141.7 (s, SꢁCꢁCHꢀCHꢁCBr). 31P{1H}-NMR (160
MHz, d8-toluene, l, −30°C); −15.6 (s, trans-PMe3),
−17.0 (d, J=14.6 Hz, cis-PMe3), −26.8 (d, J=14.6
Hz, cis-PMe3). Anal. Calc. for C16H38SBr2P4Pd2: C,
25.32; H, 5.05; S, 4.22. Found: C, 25.22; H, 5.28; S,
4.31.
−30° in a freezer to afford yellow precipitates. IR
spectrum of the precipitates showed the presence of
w(CꢂN) band in isocyanide coordinated on Pd metal.
The solution part was fully evaporated and washed
with
hexane
(1×2
ml)
to
give
trans,
trans-(Me3P)2IPdꢀC(ꢁN-n-Bu)C4H2SC(ꢁN-n-Bu)ꢀPdI-
(PMe3)2 (12) as pale yellow solids (91 mg, 69%). IR
(KBr, w(CꢁN) cm−1): 1574. 1H-NMR (300 MHz,
CDCl3, l); 0.98 (t, 6H, ꢀCH3), 1.45 (t, J=3.6 Hz, 18H,
PMe3), 1.46 (m, 4H, ꢀCH2), 1.71 (m, 4H, ꢀCH2), 3.75
(t, J=7.2 Hz, 4H, ꢀCH2), 7.54 (s, 2H, thienylene).
13C{1H}-NMR (75 MHz, CDCl3, l); 14.2 (s, CH3), 16.7
(t, J(CP)=15.4 Hz, PMe3), 21.1 (s, ꢀCH2), 33.3 (s,
ꢀCH2), 59.7 (t, J=6.3 Hz, ꢀCH2), 128.0 (s, thienylene),
151.2 (s, thienylene), 180.1(t, J(CP)=4.9 Hz, CꢁN).
31P{1H}-NMR (120 MHz, CDCl3, l); −22.0 (s). Anal.
Calc. for C26H56SI2P4Pd2: C, 30.64; H, 5.54; N, 2.75; S,
3.15. Found: C, 30.87; H, 5.89; N, 2.59; S, 3.26. Reac-
tions of t-butyl, cyclohexyl isocyanides with 5 in
CH2Cl2 were carried out analogously to give
trans,trans-(Me3P)2IPdꢀC(ꢁN-t-Bu)C4H2SC(ꢁN-t-Bu)ꢀ
PdI(PMe3)2 (13) as a pale yellow solid (49%). IR (KBr,
3.5. Reactions of CO with 5 and 7
Complex 5 (0.194 g, 0.23 mmol) was dissolved in
CH2Cl2 (2 ml) at r.t. After evacuation of the system CO
(1 atm) was introduced and the initial pale yellow
solution immediately turned to orange–yellow. After
the solution was stirred for 4 h at r.t., the solvent was
evaporated under a reduced pressure to give a yellow
residue, which was recrystallized from THF–hexane to
give a yellow solid of trans,trans-(Me3P)2IPdC(O)-
C4H2SPdI(PMe3)2 (10) (0.188 g, 94%). IR (KBr, w(CꢁO)
1
cm−1): 1598. H-NMR (300 MHz, CDCl3, l); 1.36 (t,
1
J=3.6 Hz, 18H, PMe3), 1.41 (apparent triplet, 18H,
PMe3), 6.82 (d, J=3.7 Hz, 1H, thienylene), 8.03 (d,
J=3.6 Hz, 1H, thienylene). 13C{1H}-NMR (75 MHz,
CDCl3, l); 15.6 (t, J(CP)=14.6 Hz, PMe3), 15.8 (ap-
parent triplet, PMe3), 130.2 (t, J=4.4 Hz, thienylene),
135.5 (s, thienylene), 150.8 (d, J=18 Hz, thienylene),
164.2 (t, J=9,5 Hz, thienylene), 221.6 (s, CO).
31P{1H}-NMR (120 MHz, CDCl3, l); −23.4 (s), −
26.5 (s). Anal. Calc. for C17H38SI2OP4Pd2: C, 23.18; H,
4.35; S, 3.64. Found: C, 23.23; H, 4.40; S, 3.76. Reac-
tion of CO with 7 was carried out analogously to give
trans,trans-(Et3P)2BrPdC(O)C4H2SPdBr(PEt3)2, (11) in
spectroscopic 23% yield. IR (KBr, w(CꢁO) cm−1): 1598.
1H-NMR (300 MHz, CDCl3, l); 1.10 (m, 36H,
P(CH2CH3)3), 1.81 (m, 24H, P(CH2CH3)3), 6.76 (d,
J=3.6 Hz, 1H, thienylene), 8.04 (br, 1H, thienylene).
13C{1H}-NMR (75 MHz, CDCl3, l); 8.1 (s,
P(CH2CH3)3), 8.2 (s, P(CH2CH3)3), 14.5 (apparent
w(CꢁN) cm−1): 1579. H-NMR (300 MHz, CDCl3, l);
1.44 (t, J=3.4 Hz, 18H, PMe3), 1.49 (s, 18H, ꢀCH3)
7.64 (s, 2H, thienylene). 13C{1H}-NMR (75 MHz,
CDCl3, l); 16.4 (t, J(CP)=14.5 Hz, PMe3), 31.0 (s,
ꢀCH3), 57.7 (t, J(CP)=1.5 Hz, C(CH3)3), 128.0 (s,
thienylene), 153.8 (t, J (CP)=12 Hz, thienylene), 171.4
(t, J(CP)=5.0 Hz, CꢁN). 31P{1H}-NMR (120 MHz,
CDCl3,
l);
−20.1
(s).
Anal.
Calc.
for
C26H56N2SI2P4Pd2: C, 30.64; H, 5.54; N, 2.75; S, 3.15.
Found: C, 30.87; H, 5.48; N, 2.48; S, 3.20.
trans,trans - (Me3P)2IPdꢀC(ꢁNꢀcyclohexyl)C4H2SC-
(ꢁNꢀcyclohexyl)-PdI(PMe3)2 (14) was obtained as a
pale yellow solid (60%). IR (KBr, w(CꢁN) cm−1) 1574.
1H-NMR (300 MHz, CDCl3, l); 1.46 (t, J=3.5 Hz,
18H, PMe3), 1.2–1.7 (m, 20H, ꢀC6H11), 3.89 (m, 2H,
ꢀC6H11), 7.53 (s, 2H, thienylene). 13C{1H}-NMR (75
MHz, CDCl3, l); 16.7 (t, J(CP)=15.1 Hz, PMe3), 24.5
(s, ꢀC6H11), 25.6(s, C6H11), 33.8 (s, C6H11), 67.9 (s,
C6H11), 127.9 (s, thienylene), 151.9 (t, J(CP)=8.7 Hz,
thienylene), 175.9 (t, J(CP)=4.7 Hz, CꢁN). 31P{1H}-
NMR (120 MHz, CDCl3, l); −18.9 (s). Anal. Calc. for
C30H60N2SI2P4Pd2: C, 33.63; H, 5.64; N, 2.62; S, 2.99.
Found: C, 33.87; H, 5.62; N, 2.21; S, 3.37.
triplet,
P(CH2CH3)3
15.2
(apparent
triplet,
P(CH2CH3)3. Other signals could not be observed due
to low intensity. 31P{1H}-NMR (120 MHz, CDCl3, l);
12.2 (s), 16.9 (s).
3.6. Reactions of n-butyl, t-butyl, and cyclohexyl
isocyanides with 5
3.7. X-ray structure determination
To a solution containing 5 (0.111 g, 0.13 mmol) in
THF (4 ml) was added n-butyl isocyanide (23 mg. 0.27
mmol) at r.t. The initial dark red solution immediately
turned to yellow suspension. While stirring for 3 h the
mixture turned to a yellow solution. The solution was
fully evaporated to give an oily residue and then Et2O
(2 ml) and hexane (7 ml) were added to give a yellow
solid. The solid was dissolved in Et2O and stored at
Crystals of 1, 7, and 9 suitable for X-ray crystallogra-
phy were obtained by recrystallization from tetrahydro-
furan–hexane, diethyl ether, and benzene–hexane (or
toluene–hexane) mixtures, respectively. X-ray data for
1 were collected with use of a Mac Science MXC
diffractometer equipped with an Mo X-ray tube and a
graphite crystal monochromator. X-ray data for 7 and

Y.-J. Kim et al. / Journal of Organometallic Chemistry 588 (1999) 268–277
275
gested a centrosymmetric space group and the structure
9 were collected with use of a Siemens P4 diffractome-
ter. Details on crystal and intensity data for 1, 7 and 9
are given in Table 3. For all the three crystals, three
check reflections were measured every 100 reflections
throughout data collection and showed no significant
variations in intensity. Intensity data were corrected for
Lorenz and polarization effects. Decay corrections were
also made. The intensity data were empirically cor-
rected with psi-scan data.
(
analysis converged only in P1. The structure was solved
by the direct method. All non-hydrogen atoms were
refined anisotropically, except for the carbon atoms in
the triethylphosphine (PEt3) ligands. The triethylphos-
phine carbon atoms exhibited an extremely high struc-
Table 4
Atomic coordinates (×104) and equivalent isotropic displacement
parameters (A3×103) for 1
The orientation matrix and unit cell parameters of 1
were determined from 25 machine-centered reflections
with 20°B2qB30°. All calculations for 1 were carried
out with use of the SHELX-97 [25] programs. The orien-
tation matrix and unit cell parameters of 7 and 9 were
determined from 50 reflections with 15.0°B2qB25.0°.
All calculations for 7 and 9 were carried out with use of
the Siemens SHELXTL programs [26].
The unit cell parameters and systematic absences of
1, h0l (l=2n+1) and 0k0 (k=2n+1), unambiguously
indicated P21/c as a space group. The structure was
solved by the heavy-atom method. All non-hydrogen
atoms were refined anisotropically. All hydrogen atoms
were generated in idealized positions and refined in a
riding model.
a
x
y
z
Ueq
Pd
I
S
2467(1)
3135(1)
707(1)
2618(1)
2731(1)
3722(3)
2139(1)
3090(1)
2534(5)
1323(3)
1885(9)
3064(11)
1492(9)
3521(6)
1059(6)
1705(6)
3795(7)
4079(7)
39(1)
70(1)
98(1)
50(1)
49(1)
51(1)
69(1)
85(2)
94(3)
86(2)
88(2)
68(2)
75(2)
83(2)
81(2)
2361(1)
3165(2)
3925(1)
1010(1)
2554(4)
2008(3)
2325(6)
2908(6)
4304(6)
5006(5)
3960(5)
−101(5)
866(6)
5796(2)
3008(1)
3416(2)
4970(5)
5740(3)
7051(5)
7082(7)
4348(7)
2681(9)
1835(6)
3340(8)
4845(8)
2288(8)
P(1)
P(2)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
736(6)
a Ueq is defined as one third of the trace of the orthogonalized Uij
tensor.
The unit cell parameters of 7 suggested a triclinic
space group. A statistical analysis of intensities sug-
Table 3
Crystallographic data and details of refinement of 1, 7, and 9
1
7
9
Chemical formula
Formula weight
Crystal system
Space group
C10H21IP2SPd
468.57
Monoclinic
P21/c
14.066(4)
10.941(3)
11.685(3)
C28H62Br2P4SꢀPd2
927.34
Triclinic
C16H38Br2P4SPd2·0.5C6H6
798.14
Monoclinic
P21/n
14.179(2)
15.019(2)
(
P1
,
a (A)
14.621(2)
15.839(2)
18.494(3)
74.14(1)
83.58(1)
80.92(1)
4058(1)
4
,
b (A)
,
c (A)
16.418(3)
h (°)
i (°)
k (°)
110.92(2)
115.17(1)
3
,
V (A )
Z
1679.7(8)
4
3.231
904
1.853
3164(1)
4
3.936
1592
1.686
v (mm−1
F(000)
)
3.081
1872
1.518
Dcalc. (g cm−3
)
Crystal size (mm×mm×mm)
Scan range
0.2×0.3×0.4
5°B2qB48°
3782
2477
177
ꢀ−2q
1.013
0.726, −0.667
0.377
0.532
0.0353
0.0925
0.62×0.50×0.34
3.5°B2qB50°
13042
12592
428
0.4×0.3×0.3
3.5°B2qB45°
4244
4054
240
Unique reflections
Used reflections (I]2|(I))
No. of parameters
Scan type
ꢀ
ꢀ
Goodness-of-fit on F2
1.004
1.074, −0.802
0.1910
0.3170
0.0629
1.007
−3
,
Max/min in Dz (e A
)
0.459, −0.713
0.3430
0.5085
0.0486
0.1032
Tmin
Tmax
R
a
wR2
0.1545
a wR2=ꢀ[w(Fo2−Fc2)2]/ꢀ[w(Fo2)2]1/2
.

276
Y.-J. Kim et al. / Journal of Organometallic Chemistry 588 (1999) 268–277
Table 5
Table 5 (Continued)
Atomic coordinates (×104) and equivalent isotropic displacement
3
3
a
,
parameters (A ×10 ) for 7
x
y
z
Ueq
a
x
y
z
Ueq
C(44)
C(45)
C(46)
C(47)
C(48)
C(49)
C(50)
C(51)
C(52)
C(53)
C(54)
C(55)
C(56)
11007(6)
9945(9)
−2610(6)
−477(8)
4685(4)
3600(7)
3806(9)
3010(7)
2453(9)
2304(7)
1827(9)
5339(10)
5458(9)
5938(7)
6622(8)
4883(10)
4846(11)
53(2)
103(4)
134(5)
100(4)
140(5)
101(4)
138(5)
155(6)
137(5)
104(4)
122(5)
151(6)
179(8)
Pd(1)
Pd(2)
Pd(3)
Pd(4)
Br(1)
Br(2)
Br(3)
Br(4)
S(1)
S(2)
P(1)
P(2)
P(3)
P(4)
P(5)
P(6)
P(7)
P(8)
C(1)
C(2)
C(3)
7005(1)
1386(1)
3090(1)
1408(1)
50(1)
54(1)
54(1)
56(1)
90(1)
10331(11)
10139(9)
9405(11)
11156(9)
11744(11)
13212(12)
12336(10)
12471(9)
13089(10)
14044(12)
14014(14)
227(10)
3975(1)
8692(1)
11923(1)
8089(1)
2684(1)
7358(1)
13132(1)
5417(1)
10166(1)
5865(2)
8055(2)
2962(2)
5053(2)
9788(2)
7682(2)
10819(2)
12871(2)
6179(7)
5421(9)
5495(8)
6257(11)
4817(8)
4985(11)
7842(8)
8531(10)
8163(10)
7304(12)
9243(10)
9340(13)
6175(6)
6110(6)
5447(6)
5024(6)
3324(9)
2702(11)
2899(9)
2731(10)
1769(9)
1689(11)
6168(9)
6865(10)
5094(14)
5312(13)
4660(12)
4449(17)
10742(9)
10417(12)
9356(7)
10041(9)
10321(8)
9654(10)
8113(12)
7471(14)
6611(13)
6817(19)
7330(2)
7261(14)
9757(6)
10252(6)
10946(6)
−1006(1)
6403(1)
4088(1)
2414(1)
−1701(1)
7355(1)
3325(1)
306(1)
−1998(8)
−1593(10)
−576(8)
−1091(10)
−1352(11)
−696(10)
−3003(8)
−3333(9)
−2779(11)
−3782(12)
−3583(1)
−1825(1)
1154(1)
4094(1)
93(1)
−3905(1)
−931(1)
2565(1)
−2321(1)
667(2)
100(1)
108(1)
53(1)
54(1)
66(1)
65(1)
68(1)
69(1)
64(1)
74(1)
69(1)
70(1)
80(3)
117(4)
85(3)
140(5)
88(3)
141(6)
85(3)
121(4)
120(4)
155(6)
123(5)
168(7)
55(2)
63(2)
62(2)
56(2)
103(4)
133(5)
103(4)
125(5)
102(4)
134(5)
108(4)
124(5)
182(8)
163(7)
138(5)
230(11)
100(4)
148(6)
80(3)
5340(1)
2204(1)
586(1)
2192(2)
2524(2)
3720(2)
10(1)
a Equivalent isotropic U defined as one third of the trace of the
orthogonalized Uij tensor.
−1926(1)
7286(1)
5466(2)
3214(1)
5089(1)
3176(6)
3735(8)
1902(6)
1824(9)
2297(7)
2531(9)
−399(6)
−934(8)
874(8)
−4104(2)
−2945(2)
−1230(2)
−2298(2)
184(7)
−250(9)
−218(7)
−938(10)
1424(7)
Table 6
Atomic coordinates (×104) and equivalent isotropic displacement
3
3
,
parameters (A ×10 ) for 9
a
x
y
z
Ueq
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
Pd(1)
Pd(2)
Br(1)
Br(2)
S(1)
P(1)
P(2)
P(3)
P(4)
C(1)
C(2)
C(3)
C(4)
C(11)
C(12)
C(13)
C(21)
C(22)
C(23)
C(31)
C(32)
C(33)
C(41)
C(42)
C(43)
C(6)
7604(1)
3085(1)
9332(1)
6437(1)
2893(2)
7169(2)
7961(2)
4044(2)
1493(2)
4057(8)
5006(8)
5314(9)
6275(7)
5929(8)
7159(9)
8090(9)
7036(10)
9161(9)
8117(12)
5389(8)
4148(11)
3514(11)
400(9)
5909(1)
4116(1)
5174(1)
7818(1)
5640(2)
5632(2)
6088(2)
2844(2)
3595(2)
5138(6)
5367(6)
6290(6)
6557(6)
6027(7)
4444(7)
6076(8)
6686(9)
6663(10)
5033(8)
2945(7)
2194(9)
2033(8)
4320(9)
3557(11)
2511(9)
−560(3)
20(3)
2543(1)
1889(1)
2971(1)
2075(1)
1663(2)
1050(2)
4041(2)
2149(2)
1803(2)
1916(6)
2057(6)
2020(6)
2197(6)
220(6)
43(1)
48(1)
65(1)
75(1)
61(1)
51(1)
59(1)
64(1)
61(1)
47(3)
50(3)
52(3)
44(2)
63(3)
76(3)
82(4)
95(4)
2204(10)
2562(7)
3113(9)
3201(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(37)
C(38)
C(39)
C(40)
C(41)
C(42)
C(43)
3727(11)
1680(10)
825(12)
1589(5)
1102(6)
1490(6)
2290(6)
1372(8)
1085(10)
3157(8)
4128(9)
2536(8)
1958(10)
3113(9)
3509(9)
1010(10)
605(9)
468(10)
562(5)
86(5)
−474(5)
−441(5)
546(7)
1308(8)
712(7)
818(7)
657(7)
414(8)
4321(8)
4682(8)
4600(8)
2331(8)
3116(10)
1239(9)
1154(10)
2876(9)
1349(10)
570(3)
−181(7)
−700(8)
−2045(7)
−2661(8)
−1901(11)
−1189(10)
−2930(9)
−3093(13)
7046(7)
7010(9)
8233(6)
8835(7)
7411(6)
7725(9)
4526(9)
3905(11)
5580(11)
5489(15)
5469(16)
6051(11)
5627(5)
5211(5)
4691(5)
103(5)
103(5)
78(4)
109(5)
107(5)
107(5)
115(5)
112(5)
262(15)
265(15)
320(2)
4899(13)
4955(12)
4042(11)
3150(15)
−4885(8)
−5716(11)
−4641(7)
−4947(8)
−3185(7)
−2527(10)
−2834(11)
−2377(13)
−3308(13)
−4235(18)
−1775(18)
−1441(13)
−3331(6)
−3878(6)
−3456(6)
1446(11)
955(11)
140(4)
780(3)
810(4)
C(5)
C(7)
610(3)
20(4)
520(3)
105(4)
85(3)
a Equivalent isotropic U defined as one third of the trace of the
orthogonalized Uij tensor.
135(5)
143(6)
181(8)
170(7)
270(13)
261(13)
175(7)
58(2)
tural disorder and the anisotropic refinements including
these atoms were unstable, and therefore they were
refined isotropically. All hydrogen atoms were gener-
ated in idealized positions and refined in a riding
model.
63(2)
64(2)

Y.-J. Kim et al. / Journal of Organometallic Chemistry 588 (1999) 268–277
277
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