Reactivity of the bis(silyl) palladium(II) complex toward organic isothiocyanates

Article abstract of DOI:10.1016/j.jorganchem.2010.06.013

The bis(silyl) palladium(II) complex [Pd(SiHPh₂) ₂(dmpe)] (dmpe = 1,2-bis(dimethylphosphino)ethane) reacted with organic isothiocyanates R-NCS (R = Ph, ⁱPr, allyl) to give a dithiocarbonimidato [Pd(S₂CN-Ph)(dmpe)] (1), a diphenylsilanedithiolato [Pd(S₂SiPh₂)(dmpe)] (2), or a π-allyl [(η³-allyl)Pd](NCS) (3) palladium complex, depending on the isothiocyanate type and reaction conditions. In addition, various dithiocarbonimidato Pd(II) complexes were also obtained from trans-[PdEt ₂L₂] (L = PMe₃, PMe₂Ph) (4-6) or [Pd(styrene)L₂] and organic isothiocyanates.

Full text of DOI:10.1016/j.jorganchem.2010.06.013

Journal of Organometallic Chemistry 695 (2010) 2258e2263
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Reactivity of the bis(silyl) palladium(II) complex toward organic isothiocyanates
,
a
b
b
Yong-Joo Kim a , Hyung-Tak Jeon , Kyung-Eun Lee , Soon W. Lee
*
a Department of Chemistry, Kangnung-Wonju National University, Gangneung 210-702, Republic of Korea
b Department of Chemistry, Sungkyunkwan University, Natural Science Campus, Suwon 440-746, Republic of Korea
a r t i c l e i n f o
a b s t r a c t
Article history:
The bis(silyl) palladium(II) complex [Pd(SiHPh2)2(dmpe)] (dmpe ¼ 1,2-bis(dimethylphosphino)ethane)
i
Received 20 April 2010
Received in revised form
11 June 2010
Accepted 15 June 2010
Available online 19 June 2010
reacted with organic isothiocyanates ReNCS (R ¼ Ph, Pr, allyl) to give a dithiocarbonimidato [Pd(S2C]
NePh)(dmpe)] (1), a diphenylsilanedithiolato [Pd(S2SiPh2)(dmpe)] (2), or a p-allyl [(h
3-allyl)Pd](NCS) (3)
palladium complex, depending on the isothiocyanate type and reaction conditions. In addition, various
dithiocarbonimidato Pd(II) complexes were also obtained from trans-[PdEt2L2] (L ¼ PMe3, PMe2Ph) (4e6)
or [Pd(styrene)L2] and organic isothiocyanates.
Ó 2010 Elsevier B.V. All rights reserved.
Keywords:
Palladium
Dithiocarbonimidato
Diphenylsilanedithiolato
Isothiocyanate
1. Introduction
2. Results and discussion
A stoichiometric or catalytic insertion of an organic unsaturated
compound into the MeSi bond in bis(silyl)e(group 10 metal)
complexes is a key step to generate a silyllated organic compound
[1e25]. Whereas insertion reactions of alkenes, alkynes, and dienes
are well established, those of isonitriles (ReNC), nitriles (ReCN),
and isothiocyanates (ReNCS) are still rare [26e29]. Recently, we
reported that bis(silyl) Pt(II) complexes [Pt(SiHPh2)2L2] (L ¼ tertiary
phosphine) reacted with isothiocyanates to afford the dithio-
carbonimidatoePt(II) complexes {[Pt(S2C]NR)L2] or diphenylsila-
nedithiolatoePt(II) complexes [Pt(S2SiPh2)L2]}, depending on the
reaction temperature, the stoichiometry, and the nature of the
phosphine ligand. [29]. As an extension of this study, we investi-
gated the corresponding reactivity of the Pd analogue, [Pd
(SiHPh2)2(dmpe)].
[Pd(SiHPh2)2(dmpe)] reacted with 2 equiv of PheNCS at 50 ꢀC
for 6 h in THF to give the dithiocarbonimidato Pd(II) complex [Pd
(S2C]N-Ph)(dmpe)] (1) in 77% yield (Eq. (1)). The same reaction of
1 or 2 equiv of PheNCS at room temperature did not go to
completion and gave a mixture of complex 1 and an unique
diphenylsilanedithiolato complex [Pd(S2SiPh2)(dmpe)],
2 and
a starting material. On the other hand, when the reaction was
carried out with isopropyl isothiocyanate (iPreNCS) in place of
PheNCS at room temperature, only complex 2 was obtained in 59%
yield (Eq. (2)). Complexes 1 and 2 were characterized by IR and
NMR (1H, 13C, and 31P) spectroscopy, and elemental analyses. The IR
spectra of complex 1 clearly display a new
n
(N]C) band at
1553 cmꢁ1 assignable to the S2C]NeR group, without the
n(SieH)
band at 2038 cmꢁ1 present in the starting material. 31P NMR
spectra of complexes 1 and 2 show two doublets and one singlet,
respectively, due to magnetic nonequivalence or equivalence of the
two PR2 groups. The structure of complex 2 was unambiguously
determined by X-ray diffraction.
We report herein the selective formation of the novel
dithiocarbonimidatoe
and
diphenylsilanedithiolatoePd(II)
complexes, [Pd(S2C]NR)L2] and [Pd(S2SiPh2)L2], from [Pd
(SiHPh2)2(dmpe)] and ReNCS. In order to confirm whether the
dithiocarbonimidato compound [Pd(S2C]NR)L2] can be formed by
an alternative route, we also examined the reactivity of iso-
thiocyanates with [PdEt2L2], which may serve as a source of a Pd(0)
species.
* Corresponding author. Tel.: þ82 33 640 2308; fax: þ82 33 640 2264.
E-mail address: yjkim@kangnung.ac.kr (Y.-J. Kim).
0022-328X/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.06.013

Y.-J. Kim et al. / Journal of Organometallic Chemistry 695 (2010) 2258e2263
2259
generated in situ from trans-[PdEt2L2] and styrene, gave also the same
Pd compounds. All products were characterized by spectroscopic data
and elemental analyses. The IR spectra of 4e6 display a strong C]N
band at 1552e1566 cmꢁ1 due to the dithiocarbonimidato group (S2C]
NeR). The 31P NMR data of 4e6 show two doublets due to two
Interestingly, when [Pd(SiHPh2)2(dmpe)] is treated with 2 equiv
of allyl isothiocyanate at room temperature, [(
3-allyl)Pd(dmpe)]
h
(NCS) (3) is formed in 58% yield as white crystals (Eq. (3)). The
chemical formula of complex 3 indicates that the two SiHPh2
ligands were eliminated and the CeN bond in the allyl iso-
thiocyanate was cleaved to generate the h
3-allyl ligand and the NCS
counter ion. On the other hand, the dithiocarbonimidato complex
M(S2C]Neallyl), an analogue of complex 1, is not observed. The 1H
NMR spectrum of complex 3 displays the peaks at
d
3.78 and 5.38
-allyl
due to CH2 and CH signals, respectively, characteristic of the
p
ligand. A singlet in the 31P NMR strongly supports the magnetic
equivalence of the PR2 groups in the dmpe ligand due to the high-
symmetric structure of complex 3, which was also confirmed by
X-ray diffraction.
magnetically inequivalent PR3 ligands. Molecular structures of 4 and 6
have been determined by X-ray diffraction.
The p-coordination of ReNCS into the low-valent Rh(I) [34] or Co
(0) [37] species and subsequent dimerizaion to form the five-
membered metallacycle intermediates, which ultimately go to the
dithiocarbonimidato complexes had previously been proposed. On
the basis of Eqs. (1), (2) and (4) and the foregoing proposition, we
speculate that the starting complex [Pd(SiHPh2)2L2] first undergoes
reductive elimination of Ph2HSieSiHPh2 or
to generate the Pd(0) compound, which reacts with ReNCS to form
the -coordinated intermediate [Pd(ReNCS)L2] (Scheme 1). This
a-elimination of H2SiPh2
p
intermediate reacts further with another ReNCS to give the second
intermediate, from which isocyanide (ReNC) liberates to give the
ultimate product. This speculation may explain the formal S]C bond
cleavage in ReNCS during the reaction. In the reaction mixtures in
Eqs. (1) and (2), we observed the characteristic signals assignable to
the isocyanide (R-NC) and H2SiPh2 by IR spectroscopy or GCemass
spectrometry, which are believed to be due the liberated organic
products during the reactions. However, we could not detect
Ph2HSieSiHPh2 in Eqs. (1) and (2) in the NMR and MS spectra of the
reaction mixtures. In contrast, the presence of Ph2HSieSiHPh2 in Eq.
(3) could be confirmed by mass spectrometry (ESI-TOF).
We previously observed that [Pt(SiHPh2)2(PR3)2], a Pt analogue
of the present study, reacted with AreNCS to afford the dithio-
carbonimidato Pt(II) complexes [Pt(S2C]NeAr)L2] or the diphe-
nylsilanedithiolato Pt(II) complexes Pt(S2SiPh2)2(PR3)2, depending
on the organic substrates used and supporting ligands [29]. Our
current results are basically the same as those observed for the Pt
(II) complexes; that is, the formation of dithiocarbonimidatoe or
diphenylsilanedithiolatoePd(II) complexes depends on the
substituents in the reacting isothiocyanates (aromatic versus
aliphatic). On the other hand, several Pd(0) complexes such as
[Pd2(dba)3]$CHCl3 [30] (in the presence of PPh3) and [Pd(PR3)n] [31]
(n ¼ 4 for PMe3, PMe2Ph, PMePh2; n ¼ 2 for P(i-Pr)3) were shown to
react with ReNCS (R ¼ Me, Ph, C(O)OEt) to give only the dithio-
carbonimidato Pd complexes [Pd(S2C]NeR)(PR3)2]. Several earlier
works also showed that the low-oxidation-state Pt [32], Ru [33] and
Rh [34] species reacted with isothiocyanates (ReNCS; R ¼ Me, Ph, C
(O)OEt), in the presence of excess ReNCS, to produce the dithio-
The crystal and refinement data of 2e4 and 6 are summarized in
Table 1. Fig. 1 shows the molecular structure of cis-[Pd(S2SiPh2)
(dmpe)] (2), which shows a slightly distorted square-planar coor-
dination, consisting of two PMe2 groups and two bridging sulfide
(meS) ligands that are linked to the SiPh2. The PdeS bond lengths
(2.378(6) and 2.391(6) Å) in 2 are close to those (2.362(1) and 2.392
(1) Å) in [Pd(S2SiMe2)(PEt3)2] [38,39], which was prepared from [Pd
(OAc)]2 and (SSiMe2)3. These bond lengths are comparable to the
PteS bond lengths in [Pt(S2SiPh2)(PEt3)2] (2.392(1) Å) [29], [Pt
(S2SiPh2)(PMe2Ph)2] (2.376(1) Å) [29], and [Pt(S2Si(Tbt)(Mes)
(PPh3)2] (Tbt ¼ 2,4,6-tris[bis(trimethylsilyl)]methyl)phenyl) (2.367
(15) and 2.333(17) Å) [40]. These data indicate that the dithiolatoePd
(II) complexes are less symmetric (different MeS bond lengths) than
the Pt(II) complexes having a bridged silane group, reflecting more
distorted metallacyclobutane rings containing diphenylsilyl group in
the former than those in the latter ones. Interestingly, the Pd1/Si
separation (2.9887(6) Å) is much less shorter the sum of van der
carbonimidato complexes [M(S2C]NeR)] by the
ReNCS and the (subsequent) sulfur abstraction.
p-coordination of
In order to gain insight into the formation of dithiocarbonimidato or
diphenylsilyl complexes, we further examined the chemical reactivity
of organic isothiocyanates toward other Pd compounds of tertiary
phosphines. We have already reported that reactions of trans-[PdEt2L2]
with H2SiPh2 gave the silyl-bridged dinuclear Pd complexes [Pd(m-
HSiPh2)L]2 (L ¼ PMe3, etc.) [35,36]. So, we could not use such dinuclear
silyl complexes for our study because it may cause a different reactivity
toward organic isothiocyanates. Instead, we tried to examine direct
reactions of diethyl Pd(II) complexes with isothiocyanates. Trans-
[PdEt2L2] (L ¼ PMe3, PMe2Ph) were treated directly with 2 equiv or
excess ReNCS at room temperature, and the corresponding dithio-
carbonimidato Pd(II) complexes could be obtained in 49e90% yields
(Eq. (4)). Similar reactions employing [Pd(styrene)L2], which is
N
R
S
L
L
L
L
L
L
S
S
R-N=C=S
S
Pd
Pd
S
Pd
N
C
N
R
R
C
N R
N
R
Scheme 1.

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Y.-J. Kim et al. / Journal of Organometallic Chemistry 695 (2010) 2258e2263
Table 1
X-ray data collection and structure refinement for 2e4 and 6.
2
3
4
6
Formula
fw
C18H26P2PdS2Si
502.94
C10H21NP2PdS
355.68
C13H23NP2PdS2
425.78
C23H27NP2PdS2
549.92
Temperature, K
Crystal size (mm3)
Crystal system
Space group
a, Å
296(2)
296(2)
296(2)
296(2)
Orthorhombic
Pna21
16.0226(14)
15.5152(14)
8.8319(8)
90
Orthorhombic
P212121
9.1802(2)
9.5367(2)
17.1700(4)
90
Orthorhombic
P212121
9.8909(1)
10.1830(1)
18.0201(2)
90
Triclinic
P1
9.7110(2)
9.9037(2)
13.2588(2)
106.599(1)
95.102(1)
91.354(1)
1215.57(4)
2
b, Å
c, Å
a
, deg
, deg
b
90
90
90
90
90
90
g
, deg
V, Å3
2195.6 (3)
4
1.522
1503.21(6)
4
1.572
1814.97(3)
4
1.558
Z
dcal, g cmꢁ3
1.502
1.077
m
, mmꢁ1
0.235
1.559
1.417
F(000)
1024
720
864
560
Tmin
Tmax
0.7083
0.8461
53,702
5389
0.5743
0.6192
30,978
3703
0.8484
0.8951
21,186
4479
0.7821
0.8816
10,397
5921
No. of reflns measured
No. of reflns unique
No. of reflns with I > 2
No. of params refined
s
(I)
4869
218
0.348
3499
220
0.409
3980
173
0.454
5069
262
0.369
Max. in Dr (e Åꢁ3
)
Min. in Dr (e Åꢁ3
GOF on F2
R1a
)
ꢁ0.169
ꢁ0.433
ꢁ0.319
ꢁ0.301
1.035
1.059
1.024
1.024
0.0204
0.0423
0.0184
0.0461
0.0294
0.0558
0.0269
0.0598
wR2b
a
R1 ¼ S[jFoj ꢁ jFcj]/SjFoj].
b
wR2 ¼ S[w(F2o ꢁ F2c)2]/S[w(F2o)2]1/2
.
Waals radii of Pd (1.63 Å) and Si (2.10 Å) atoms, indicating a very
These reactions gave the novel dithiocarbonimidato Pd(II) complex
[(PdS2C]NPh)(dmpe)], the diphenylsilanedithiolato Pd(II)
complex [Pd(S2SiPh2)(dmpe)], and a -allyl complex [(
3-allyl)Pd
(dmpe)](NCS) by sulfur abstraction from organic isothiocyanates
and the silyl elimination. We alternatively prepared dithiocarbo-
nimidato complexes, [Pd(S2C]NeR)L2].
strong van der Waals contact or an elongated PdeSi bond.
The ORTEP drawing of [(
clearly reveals a square plane consisting of a chelating phosphine
(dmpe) and a -allyl fragment around the Pd center. On the other
h
3-allyl)Pd(dmpe)](NCS) (3) in Fig. 2
p
h
p
hand, Figs. 3 and 4 show the molecular structure of dithiocarbo-
nimidato Pd(II) complexes (4 and 6), whose PdeS bond lengths
(2.314(7)e2.344(7) Å) are similar to those (2.310(5)e2.343(1) Å)
observed for other dithiocarbonimidato Pd(II) complexes, [Pd
(S2CNeCH2Ph)(PEt3)2] [41,42] and [Pd(S2CNCOOEt)(PPh3)2] [30].
In summary, we carried out several reactions of the bis(silyl) Pd
(II) complex [Pd(SiHPh2)2(dmpe)] with organic isothiocyanates.
3. Experimental
General Methods. All manipulations of air-sensitive compounds
were performed under N2 or Ar by standard Schlenk-line tech-
niques. Solvents were distilled from Na-benzophenone. Analytical
Fig. 1. ORTEP drawing of 2 showing the atom-labeling scheme and 50% probability thermal ellipsoids. Selected bond lengths (Å) and angles (ꢀ): Pd1eP2 2.2405(6), Pd1eP1 2.2473
(6), Pd1eS2 2.3775(6), Pd1eS1 2.3961(6), S1eSi1 2.1041(8), S2eSi1 2.1005(8); P2ePd1eP1 85.52(2), P2ePd1eS2 90.79(2), P1ePd1eS2 176.29(2), S2ePd1eS1 88.48(2), S i1eS1ePd1
82.96(2), Si1eS2ePd1 83.49(2).

Y.-J. Kim et al. / Journal of Organometallic Chemistry 695 (2010) 2258e2263
2261
solution was completely evaporated under vacuum, and then the
oily residue was solidified with n-hexane. The solids were filtered
and washed with hexane (2 ꢂ 2 ml). Recrystallization from ether/
CH2Cl2 (3:1) gave white crystals of [Pd(S2C]NePh)(dmpe)], (1,
0.227 g, 77%). IR (KBr, cmꢁ1): (CN) 1553. 1H NMR (DMSO-d6,
n d):
1.57 (dd, J ¼ 11, 19 Hz, 12H, PMe2), 2.07 (d, J ¼ 19 Hz, 4H, P-CH2),
6.80e6.83 (m, 3H, Ph), 6.89e6.94 (m, 2H, Ph). 13C{1H} NMR (DMSO-
d6,
d
): 11.1 (d, JPeC ¼ 25 Hz, PMe2), 26.9 (dd, JPeC ¼ 15, 32 Hz, PCH2),
121.9, 128.2, 148.3, 179.2 (CN). 31P{1H} NMR (DMSO-d6,
d
): 40.1(d,
J ¼ 36 Hz), 40.8 (d, J ¼ 36 Hz). Anal. Calcd for C13H21NP2S2Pd: C,
36.84; H, 4.99; N, 3.30. Found: C, 36.84; H, 5.18; N, 2.99.
The collected filtrates were analyzed by IR spectroscopy and
GCemass spectrometry. Their IR spectra show the characteristic
bands assignable to the C^N bond in isocyanide at 2164 cmꢁ1 and
the SieH bond in H2SiPh2 at 2102 cmꢁ1. MS: 103 (Mþ) (for
C^NePh) and 184 (Mþ) (for H2SiPh2).
To a Schlenk flask containing [Pd(SiHPh2)2(dmpe)] (0.351 g,
0.563 mmol) was added THF (4 ml) and iPreNCS (0.114 g,
1.13 mmol) at room temperature. The reaction mixture was stirred
for 16 h to give a yellow precipitate. The solids were filtered and
washed with hexane (2 ꢂ 2 ml) (0.166 g, 59%). Recrystallization of
[Pd(S2SiPh2)(dmpe)] (2) from ether/CH2Cl2 (3:1) gave white crys-
Fig. 2. ORTEP drawing of 3. Selected bond lengths (Å) and angles (ꢀ): Pd1eC2 2.149(2),
Pd1eC3 2.171(2), Pd1eC1 2.183(2), C1eC2 1.384(4), C2eC3 1.386(4), Pd1eP2 2.2761(6),
Pd1eP1 2.2768(5); C3ePd1eC1 67.53(10), P2ePd1eP1 87.31(2), N1eC10eS1 177.3(9).
tals suitable for X-ray diffraction study. 1H NMR (DMSO-d6,
(d, J ¼ 12 Hz, 12H, PMe2), 2.04 (d, J ¼ 20 Hz, 4H, P-CH2), 7.25e7.30
(m, 6H, Ph), 7.58e7.62 (m, 4H, Ph). 13C{1H} NMR (DMSO-d6,
): 12.9
(dt, JPeC ¼ 7.4, 28 Hz, PMe2), 26.9 (dd, JPeC ¼ 22 Hz, PCH2), 126.9,
128.0, 132.9, 145.8. 31P{1H} NMR (DMSO-d6,
): 47.6. Anal. Calcd for
d): 1.61
d
laboratory at Kangneung-WonJu National University carried out
elemental analyses. IR spectra were recorded on a Perkin Elmer BX
spectrophotometer. GC-MS was performed on a Agilent 6890
GC/5973i MSD. Exact mass was measured on a ESI-TOF API QSTAR
Pulsar I. NMR (1H, 13C{1H}, and 31P{1H}) spectra were obtained on
JEOL Lamda 300 MHz spectrometer. Chemical shifts were refer-
enced to internal Me4Si (1H and 13C{1H}) or external 85% H3PO4
d
C18H26P2S2SiPd: C, 42.98; H, 5.21; S, 12.75. Found: C, 42.63; H, 5.51;
S, 12.29.
Ph2SiHSiHPh2: MS (ESI-TOF) Calcd for C24H22Si2 (M þ H)þ:
367.1338. Found for 367.2867
(
31P{1H}). PheNCS, CH2]CHCH2NCS, and iPreNCS were purchased.
3.2. Preparation of the complex 3
[Pd(SiHPh2)2L2] (L2 ¼ dmpe) [43] and trans-PdEt2L2 (L ¼ PMe3,
PMe2Ph) [44,45] were prepared by the literature methods.
At room temperature, THF (5 ml) and CH2]CHCH2NCS (0.105 g,
1.06 mmol) were added to [Pd(SiHPh2)2(dmpe)] (0.331 g,
0.53 mmol). The reaction mixture was stirred overnight to give
a yellow precipitate. The resulting solids were filtered and washed
with hexane (2 ꢂ 2 ml). The filtrate was completely evaporated
under vacuum, and then the oily residue was solidified with
n-hexane. The collected solids were recrystallized from n-hexane/
3.1. Preparation of complexes 1 and 2
To a Schlenk flask containing [Pd (SiHPh2)2(dmpe)] (0.435 g,
0.697 mmol) was added THF (4 ml) and PheNCS (0.189 g,
1.39 mmol). After stirring for 6 h at 50 ꢀC, the resulting orange
Fig. 3. ORTEP drawing of 4. Selected bond lengths (Å) and angles (ꢀ): Pd1eP1 2.2915(7), Pd1eP2 2.2959(8), Pd1eS1 2.3143(7), Pd1eS2 2.3440(7), S1eC1 1.758(3), S2eC1 1.762(3),
N1eC1 1.261(4), N1eC2 1.418(4); P1ePd1eP2 97.49(3), P1ePd1eS1 92.95(3), P2ePd1eS2 93.90(3), S1ePd1eS2 75.50(3), C1eS1ePd1 88.61(9), C1eS2ePd1 87.59(9), C1eN1eC2
123.1(3), N1eC1eS1 121.6(2), N1eC1eS2 130.1(2), S1eC1eS2 108.23(15).

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Y.-J. Kim et al. / Journal of Organometallic Chemistry 695 (2010) 2258e2263
Fig. 4. ORTEP drawing of 6. Selected bond lengths (Å) and angles (ꢀ): Pd1eP1 2.2922(5), Pd1eP2 2.2996(6), Pd1eS1 2.3197(6), Pd1eS2 2.3335(5), S1eC1 1.752(2), S2eC1 1.765(2);
P1ePd1eP2 98.27(2), P1ePd1eS1 168.26(2), P2ePd1eS1 92.05(2), P1ePd1eS2 94.93(2), P2ePd1eS2 165.21(2), S1ePd1eS2 75.55(2), C1eS1ePd1 88.45(7), C1eS2ePd1 87.71(7),
N1eC1eS1 121.4(2), N1eC1eS2 130.3(2), S1eC1eS2 108.3(1).
CH2Cl2 (5:1) to form white crystals of complex 3 (0.189 g, 58%). IR
(KBr, cmꢁ1): (NCS) 2054. 1H NMR (CDCl3,
): 1.78 (m, 12H, PMe2),
Complex 4 was prepared in another way. To a Schlenk flask
containing trans-PdEt2(PMe3)2 (0.278 g, 0.878 mmol) at 0 ꢀC were
added sequentially styrene (0.274 g, 2.63 mmol) and THF (2 ml).
The mixture was heated at 55 ꢀC for 1 h to give a yellow solution. At
room temperature, on addition of PheNCS (0.119 g, 0.878 mmol) to
the mixture, the yellow solution turned to an orange one. After
stirring for 16 h at room temperature, the solvent was completely
removed under vacuum, and then the resulting residue was solid-
ified with n-hexane. The resulting white solids were filtered,
washed with n-hexane (2 ꢂ 2 ml) and dried under vacuum to give 4
(0.426 g, 59%). Complexes 5 and 6 were analogously prepared.
Complexes 4 and 6 were also independently prepared from the
reactions of PdL4 (L ¼ PMe3, PMe2Ph) with PheNCS [31].
n
d
2.12 (d, J ¼ 17 Hz, 4H, PCH2), 3.78(br, 4H, CH2), 6.38 (qnt, J ¼ 11H,1H,
CH). 13C{1H} NMR (CDCl3): 15.3 (dt, JPeC ¼ 12, 126 Hz, PMe2), 28.8
(dd, JPeC ¼ 22, 24 Hz, PCH2), 66.0 (t, JPeC ¼ 17 Hz, CH2), 121.6 (t,
JPeC ¼ 5.9 Hz, CH). 31P{1H} NMR (CDCl3): 29.7(s). Anal. Calcd for
C10H19NP2SPd: C, 33.76; H, 5.95; N, 3.94. Found: C, 33.94; H, 6.05;
N, 3.67.
3.3. Preparation of complexes 4e6
These complexes were prepared in the same way. To a Schlenk
flask containing trans-PdEt2(PMe3)2 (0.458 g, 1.45 mmol) was
added PheNCS (0.391 g, 2.89 mmol) and THF (4 ml). The reaction
mixture was stirred overnight at room temperature to give yellow
precipitates, which were filtered and washed with hexane
(2 ꢂ 2 ml). Recrystallization from n-hexane/CH2Cl2 (3:1) gave
3.4. X-ray structure determination
white crystals of complex 4 (0.303 g, 49%). IR (KBr, cmꢁ1):
n
(CN)
All X-ray data were collected with a Bruker Smart APEX2
diffractometer equipped with a Mo X-ray tube. Collected data were
corrected for absorption with SADABS based upon the Laue
symmetry by using equivalent reflections [46]. All calculations
were carried out with SHELXTL programs [47]. All structures were
solved by direct methods. All non-hydrogen atoms were refined
anisotropically, and all hydrogen atoms were generated in ideal
positions and refined in a riding model.
1563. 1H NMR (CDCl3,
d
): 1.48 (d, J ¼ 9.5, 9H, PMe3), 1.54 (d, J ¼ 9.5,
9H, PMe3), 6.98e7.04 (m, 1H, Ph), 7.08e7.11 (m, 2H, Ph). 7.23e7.29
(m, 2H, Ph). 13C{1H} NMR (CDCl3): 16.2 (ddd, JPeC ¼ 6.5, 16 Hz,
PMe3), 122.2, 122.9, 128.3, 147.5, 175.8 (CN). 31P{1H} NMR (CDCl3):
ꢁ16.2(d, J ¼ 51 Hz), ꢁ16.7 (d, J ¼ 51 Hz). Anal. Calcd for
C13H23NP2S2Pd: C, 36.67; H, 5.44; N, 3.29. Found: C, 36.64; H, 5.65;
N, 3.26.
Data for [Pd(S2C]NeEt)(PMe3)2], (5, 57%). IR (KBr, cmꢁ1):
n
(CN)
1566. 1H NMR (CDCl3,
d
): 1.25 (t, J ¼ 7.1 Hz, 3H, CH3), 1.53 (d,
Acknowledgment
J ¼ 9.0 Hz, 18H, PMe3), 3.66 (q, J ¼ 7.3 Hz, 2H, CH2), 6.98e7.04 (m,
1H, Ph), 7.08e7.11 (m, 2H, Ph). 7.23e7.29 (m, 2H, Ph). 13C{1H} NMR
(CDCl3): 16.2 (ddd, JPeC ¼ 5.0, 13 Hz, PMe3), 15.8 (s, CH3), 42.2 (s,
CH2), 171.0 (s, CN). 31P{1H} NMR (CDCl3): ꢁ16.6 (d, J ¼ 51 Hz), ꢁ17.3
(d, J ¼ 51 Hz). Anal. Calcd for C9H23NP2S2Pd: C, 28.61; H, 6.13; N,
3.71. Found: C, 28.83; H, 6.41; N, 3.30.
This work was supported by National Research Foundation of
Korea Grant funded by the Korean Government (KRF-2008-313-
C00452).
Data for [Pd(S2C]NePh)(PMe2Ph)2], (6, 90%). IR (KBr, cmꢁ1):
n
Appendix A. Supplementary data
(CN) 1552. 1H NMR (CDCl3,
d): 1.41 (d, J ¼ 9.3 Hz, 6H, PMe2), 1.48 (d,
J ¼ 9.3 Hz, 6H, PMe2), 7.00e7.06 (m, 1H, Ph), 7.15e7.19 (m, 2H, Ph).
7.26e7.45 (m, 2H, Ph). 13C{1H} NMR (CDCl3): 14.0 (ddd, JPeC ¼ 5.0,
20 Hz, PMe2), 122.3, 122.9, 128.3, 128.7, 128.8, 128.9, 129.0, 130.5,
130.6, 133.3, 147.4, 175.8 (s, CN). 31P{1H} NMR (CDCl3): ꢁ6.89 (d,
J ¼ 49 Hz), ꢁ7.49 (d, J ¼ 49 Hz). Anal. Calcd for C23H27NP2S2Pd: C,
48.98; H, 4.83; N, 4.97. Found: C, 49.07; H, 4.92; N, 4.87.
CCDC No. 783248-783251 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of charge
from the Cambridge Crystallographic Data centre via www.ccdc.ac.
uk/data-request/cif. Supplementary data associated with this article
can be found in the online version, at doi: 10.1016/j.jorganchem.2010.
06.013.

Y.-J. Kim et al. / Journal of Organometallic Chemistry 695 (2010) 2258e2263
[26] M. Tanabe, K. Osakada, Organometallics 20 (2001) 2118.
2263
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