Reactivities of organic isothiocyanates and thiocyanates toward dialkyl bis(phosphine) complexes of palladium(II) and platinum(II)

Article abstract of DOI:10.1016/j.poly.2014.10.020

Room-temperature reactions of trans-[PdEt₂L₂] (L = PMe₃, PEt₃, PMe₂Ph) with organic isothiocyanates [R-NCS; R = benzyl; CH(CH₃)Ph, R-(-) and S-(+); indanyl, S-(+)] afforded the S,S-coordinated Pd(II) complexes [Pd(S₂CN-R)L₂] containing a dithiocarbonimidato (S₂CN-R) group. Similar reactions involving allyl isothiocyanates produced the cationic η³-allyl Pd complex [Pd(η³-allyl)(PMe₃)₂]⁺(NCS)^-. When [Pd(S₂CN-R)(PMe₃)₂] was treated with 1 equiv of a chelating phosphine [L-L = depe (1,2-bis(diethylphosphino)ethane) and dmpe (1,2-bis(dimethylphosphino)ethane)], the corresponding complexes [Pd(S₂CN-R)(L-L)] were produced. Reactions of trans-[PdEt₂L₂] (L = PMe₃, PMe₂Ph) with organic thiocyanates (R-SCN; R = benzyl, Et) resulted in the formation of [Pd(CN)₂L₂] and an organic disulfide by S-C bond cleavage of R-SCN. However, similar reactions of the dimethyl analogs, trans-[PdMe₂L₂] (L = PMe₃, PEt₃), with benzyl thiocyanate afforded different products, [Pd(NCS)₂L₂] or [PdMe(NCS)L₂]. Treating [Pt(styrene)(PMe₃)₂] with benzyl isothiocyanate gave the S-coordinated dithiocarbonimidato Pt(II) complex, [Pt(S₂CN-R)(Me₃P)₂] (R = benzyl). In contrast, cis-[PtEt₂(PMe₃)₂] reacted with the isothiocyanate to afford the trialkyl Pt(IV) complex [PtEt₂(SCN)(CH₂Ph)(PMe₃)₂].

Full text of DOI:10.1016/j.poly.2014.10.020

Accepted Manuscript
Reactivities of organic isothiocyanates and thiocyanates toward dialkyl
bis(phosphine) complexes of palladium(II) and platinum(II)
Seon Gye Lee, Keun-Young Choi, Yong-Joo Kim, SuJin Park, Soon W. Lee
PII:
S0277-5387(14)00682-2
DOI:
http://dx.doi.org/10.1016/j.poly.2014.10.020
POLY 11033
Reference:
Polyhedron
To appear in:
Received Date:
Accepted Date:
2 September 2014
19 October 2014
Please cite this article as: S.G. Lee, K-Y. Choi, Y-J. Kim, S. Park, S.W. Lee, Reactivities of organic isothiocyanates
and thiocyanates toward dialkyl bis(phosphine) complexes of palladium(II) and platinum(II), Polyhedron (2014),
doi: http://dx.doi.org/10.1016/j.poly.2014.10.020
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(revised to polyhedron)
Reactivities of organic isothiocyanates and thiocyanates toward dialkyl
bis(phosphine) complexes of palladium(II) and platinum(II)
Seon Gye Leea, Keun-Young Choia, Yong-Joo Kima,*, SuJin Parkb, Soon W. Leeb
aDepartment of Chemistry, Kangnung-Wonju National University, Gangneung 210-702,
Korea
bDepartment of Chemistry, Sungkyunkwan University, Suwon 440-746, Korea
(Received
)
__________________________
* Corresponding author: E-mail: yjkim@ kangnung.ac.kr
Tel: + 82 + 33-640-2308
Fax: + 82 + 33-640-2264
1

Abstract
Room-temperature reactions of trans-[PdEt2L2] (L = PMe3, PEt3, PMe2Ph) with organic
isothiocyanates [R–NCS; R = benzyl; CH(CH3)Ph, R-(−) and S-(+); indanyl, S-(+)]
afforded the S,S-coordinated Pd(II) complexes [Pd(S2C=N–R)L2] containing a
dithiocarbonimidato (S2C=N–R) group. Similar reactions involving allyl
isothiocyanates produced the cationic η3-allyl Pd complex [Pd(η3-allyl)
(PMe3)2]+(NCS)−. When [Pd(S2C=N–R)(PMe3)2] was treated with 1 equiv of a chelating
phosphine [L~L
=
depe (1,2-bis(diethylphosphino)ethane) and dmpe (1,2-
bis(dimethylphosphino)ethane)], the corresponding complexes [Pd(S2C=N–R)(L~L)]
were produced. Reactions of trans-[PdEt2L2] (L = PMe3, PMe2Ph) with organic
thiocyanates (R–SCN; R = benzyl, Et) resulted in the formation of [Pd(CN)2L2] and an
organic disulfide by S–C bond cleavage of R–SCN. However, similar reactions of the
dimethyl analogs, trans-[PdMe2L2] (L = PMe3, PEt3), with benzyl thiocyanate afforded
different products, [Pd(NCS)2L2] or [PdMe(NCS)L2]. Treating [Pt(styrene)(PMe3)2]
with benzyl isothiocyanate gave the S-coordinated dithiocarbonimidato Pt(II) complex,
[Pt(S2C=N–R)(Me3P)2] (R = benzyl). In contrast, cis-[PtEt2(PMe3)2] reacted with the
isothiocyanate to afford the trialkyl Pt(IV) complex [PtEt2(SCN)(CH2Ph)(PMe3)2].
_____________________________________________
Key words: Organic Isothiocyanate, Organic Thiocyanate, Oxidative Addition,
Palladium, Platinum
Introduction
Organic isothiocyanates (R–NCS), a family of pseudohalides, are widely used for
the synthesis of heterocyclic compounds via cycloaddition with organic unsaturated
compounds or main-group metal complexes containing unsaturated ligands [1–7]. These
species also react with transition-metal complexes bearing pseudohalo [8–16], halo [17–
19], unsaturated [20], hydrido [21], silyl [22], and sulfido ligands [23] to form N or S-
coordinated heterocycles or metallacycles. Organolanthanide complexes also undergo
analogous reactions with organic isothiocyanates [24]. In particular, certain organic
isothiocyanates react with zero-valent Co, Rh, Ru, Pd, and Pt complexes to afford S-
coordinated metallacycles or cycloaddition products [25–29]. Our group also observed
2

the same reactivity in reactions involving group 10 metal azide [13] or silyl complexes
[22].
In this study, we attempted to extend the scope of the above-mentioned reactions
by investigating the reactions of organic pseudohalides with dialkyl Pd(II) and Pt(II)
complexes. To the best of our knowledge, the oxidative addition and cycloaddition of
pseudohalides to transition-metal–alkyl complexes have been little studied to date. Here,
we report Pd–S, Pd–N, and Pt–N bond formation observed in reactions between dialkyl
Pd(II) or Pt(II) complexes and organic isothiocyanates or thiocyanates.
Results and Discussion
Reactions of organic isothiocyanates (R–NCS) with dialkyl Pd(II) complexes
We previously demonstrated that disilyl bis(phosphine) complexes of Pd(II) and
Pt(II), [M(SiHPh2)2L2], react with aryl isothiocyanates (Ar–NCS) to afford the S-
coordinated dithiocarbonimidato complexes, [M(S2C=N–Ar)L2] [22]. As an extension
of that study, the reactions of trans-[PdEt2L2] (L = PMe3, PMe2Ph), a dialkyl analog,
with alkyl isothiocyanates were examined. As expected, these dialkyl species react with
2 equiv of isothiocyanates to afford S-coordinated dithiocarbonimidato Pd(II)
complexes, [Pd(S2C=N–R)L2] (complexes 1–6), in moderate to good yields (Eq. 1 in
Scheme 1). However, the absolute configurations of the products obtained from chiral
isothiocyanates could not be unambiguously assigned on the basis of spectroscopic data.
Several attempts were therefore made to obtain crystals for X-ray diffraction, but these
were unsuccessful. To overcome this problem, we synthesized complexes containing a
single chelating phosphine from the corresponding bis(monodentate) phosphine
complexes by ligand replacement, and then confirmed their absolute configurations by
X-ray diffraction. The bis(trimethylphosphine) Pd(II) complexes [Pd(S2C=N–
R)(PMe3)2] reacts slowly with 1 equiv of a chelating phosphine ligand (L~L = depe or
dmpe) to give Pd complexes with one chelating phosphine, [Pd(S2C=N–R)(L~L)]
(complexes 7–9, Eq. 2 in Scheme 1).
3

L
L
S
S
Et
L
R-N=C=S
(1)
Pd
N
Pd
R
L
Et
L = PMe3
R = CH2Ph, 57 %, 1
R = CH(CH3)Ph (R,-), 2
3
R = CH(CH3)Ph (S,+),
4
R = Indanyl (S,+),
R = CH(CH3)Ph (R,-),
R = CH(CH3)Ph (S,+), 6
5
L = PMe2Ph
L
L
S
S
L
L
S
L ~ L
- 2 L
Pd
N
Pd
N
(2)
R
R
S
7
L = PMe3 R = CH(CH3)Ph (R,-); L~L = depe,
R = CH(CH3)Ph (S,+); L~L = depe,
R = CH(CH3)Ph (R,-); L~L = dmpe,
8
9
Scheme 1
The IR spectra of complexes 1–9 display a strong N=C bond stretching vibration
at 1550–1570 cm−1. The PMe3 and PR2 regions in the 13C{1H} NMR spectra show
doublets of two doublets. The 31P{1H} NMR spectra also display two doublets,
indicating asymmetric S,S’-coordination of the dithiocarbonimidato ligand to the Pd
center. The molecular structures of [Pd{(R)-(−)-S2C=NC(H)(Me)(Ph)}(depe)] (7)
(Figure 1) and [Pd{(S)-(+)-S2C=NC(H)(Me)(Ph)}(depe)] (8) (Figure 2) clearly show the
formation of Pd(II) complexes containing a dithiocarbonimidato ligand with an chiral
moiety (R,− or S,+), whose absolute configuration remained unchanged during the
reaction, as expected. In complexes 7 and 8, the Pd metal has a slightly distorted square-
planar geometry and coordinates to two sulphur atoms (the dithiocarbonimidato ligand)
and two phosphorus atoms (depe).
In earlier work on several reactions of Pd(0) complexes with R–NCS (R = Me,
Ph) and EtOCONCS), S-coordinated dithiocarbonimidato Pd(II) complexes were
obtained [26,27]. In addition, low-oxidation-state Pt [25,28], Ru [29], and Rh [17]
species reacted with isothiocyanates (R–NCS; R = Me, Ph, C(O)OEt) to afford the
dithiocarbonimidato complexes. As mentioned above, we also reported that bis(silyl)
Pd(II) and Pt(II) complexes react with aryl isothiocyanates to afford the corresponding
dithiocarbonimidato Pd(II) and Pt(II) complexes depending on the isothiocyanates used
[22]. These observations suggest that Pt(0) and Pd(0) species are key intermediates or
4

starting materials for cycloaddition of isothiocyanates. The formation of complexes 1–6
can be explained on the basis of the known mechanism of dithiocarbonimidato Pd(II)
complexes formation, i.e., a combination of coordination of two R–NCS ligands to a
Pd(0) center to form a metallacyclic intermediate, and subsequent elimination of an
organic isocyanide ( Scheme 2).
Interestingly, the reaction with allyl isothiocyanate afforded a cationic η3-allyl Pd
complex, [Pd(η3-allyl)(PMe3)2]+(NCS)− (10), which was characterized by NMR
spectroscopy and elemental analysis (Scheme 3). The moisture-sensitive complex 10
was obtained as a white solid. The originally expected dithiocarbonimidato Pd(II)
complex, [Pd(S2C=N–allyl)(η3-allyl)(PMe3)2], was not observed. It is worth noting that
allyl halides and pseudohalides have been used for the preparation of η3-allyl
complexes; for example, Boersma and co-workers [30] showed that the reaction of
[PdMe2(tmeda)] (tmeda = tetramethylethylenediamine) with allyl bromide at room
temperature affords a cationic complex, [Pd(η3-allyl)(tmeda)]Br. In addition, Wilkinson
et al. [25] proposed the presence of [Pt(η3-allyl)(PPh3)2](SCN) in solution during the
reaction of [Pt(PPh3)3] with allyl isothiocyanate.
5

Reactions of organic thiocyanates (R–SCN) with dialkyl Pd(II) complexes
In order to compare the chemical reactivities between R–NCS and R–SCN toward
dialkyl bis(phosphine) Pd(II) complexes, we examined reactions involving organic
thiocyanates (R–SCN). The addition of 2 equiv of R–SCN (R = benzyl or ethyl) to
trans-[PdEt2L2] (L = PMe3, PMe2Ph) gave an unexpected product, [Pd(CN)2L2], as well
as an organic dithiolato compound (R–S–S–R) (Scheme 4). However, pseudohalogen
products, the thiocyanato complex [Pd(SCN)2L2] and the isothiocyanato complex
[Pd(NCS)2L2], were not observed. Complexes 11 and 12 are formed by either of two
three-step reactions (Scheme 4), both of which involve a Pd(0) intermediate formed by
R–R reductive elimination (β-H elimination). The first possible pathway involves trans
or cis S–C oxidative addition of R–SCN to the Pd(0) intermediate to afford the Pd(IV)
intermediate; trans addition is more plausible because of the C–S bond polarity. In the
subsequent step, the intermediate reductively eliminates R–S–S–R, with the formation
of [Pd(CN)2L2]. The second possible pathway involves oxidative addition of R–SCN to
the Pd(0) intermediate (L2Pd), followed by electrophilic attack of another R–SCN at the
SR ligand. The second pathway also explains the formation of the final products.
Ogawa and co-workers [31] showed that Ph–SCN oxidatively adds to [Pd(PPh3)4] to
afford [Pd(CN)(SPh)(PPh3)2]. It is worth mentioning that the oxidative addition or
reductive elimination of organic halides to zero-valent transition-metal complexes has
been extensively studied, but those involving organic pseudohalides are relatively rare.
6

The IR spectra of [Pd(CN)2(PR3)2] display a sharp absorption band at 2123–2126
cm−1 from the CN group, which agrees well with those in known bis(cyanato) Pd(II)
complexes [13d]. To gain an insight into the possible intermediate in Scheme 4, trans-
[PdEt2L2] was treated with 2 equiv of benzyl mercaptan to give the bis(thiolato) Pd(II)
complex trans-[Pd(SCH2Ph)2(PMe3)2] (13) (Scheme 5). This product was characterized
using spectroscopy and X-ray diffraction (Figure 3).
For comparison, we investigated similar reactions involving cis-[PdMe2L2] (L =
PEt3, PMe3; Scheme 6). In the case of cis-[PdMe2(PEt3)2], the reaction smoothly
proceeded to afford trans-[PdMe(NCS)(PEt3)2] (14) in 50% yield and a mixture of
organic products (PhCH2SMe, 12%; PhCH2CH2Ph, 10%; PhCH2SCH2Ph, 10%) (Eq.1
in Scheme 6). In contrast, the reaction involving cis-[PdMe2(PMe3)2], a PMe3 analog,
produced a mixture of a bis(isothiocyanato) Pd(II) complex, trans-[Pd(NCS)2(PMe3)2]
(15, 33% yield), as the major product, and trans-[PdMe(NCS)(PMe3)2] (16, less than
1% yield) as a minor product, as well as organic products (PhCH2Me, 4%;
PhCH2CH2Ph, 16%; PhCH2SCH2Ph, 18%; PhCH2SSCH2Ph, 17%; Eq. 2 in Scheme 6).
7

In the IR and NMR spectra of the crude product in Eq. 1, we observed the CN
band of NCS at 2095 cm−1 for the major product and the CN band at 2149 cm−1 for an
unidentified minor product. The GLC and GC–MS data confirmed R–R, RS–R, and
RS–Me as organic products. After recrystallization, pure trans-[PdMe(NCS)(PEt3)2]
(14) was obtained. The IR spectra of the final products in Eq. 2 showed a strong NCS
band at 2091 cm–1 for the major product (15). Unfortunately, the IR bands of the NCS
1
ligands of complexes 15 and 16 in Eq. 2 overlapped. However, the H NMR spectra of
the products clearly displayed a triplet at δ −0.19 ppm (JPH = 6.9 Hz) from the Pd–Me
bond and a triplet at δ 1.49 ppm (JPH = 3.6 Hz) from the Pd–PMe3 bond, confirming the
stereochemistry of complex 16.
These results (Scheme 6) indicate that the reactivity of R–SCN toward cis-
[PdMe2(PMe3)2] is more complicated than that toward cis-[PdMe2(PEt3)2]; i.e., the
reactivity appears to depend on the identity of the phosphine ligand. At present,
however, we are unable to provide a clear mechanism for these reactions..
Reactions of organic thiocyanates (R–SCN) with dialkyl Pt(II) complexes
In order to examine the difference between the reactivites of Pd(II)- and Pt(II)
dialkyl complexes, we performed reactions of cis-[PtR2(PR3)2] (R = Me, Et; PR3 =
PMe3, PEt3) with organic isothiocyanates and thiocyanates. Several attempts to isolate
the products from the reactions of cis-[PtMe2(PR3)2] with 2 equiv of benzyl
isothiocyanate (PhCH2–NCS) and thiocyanate (PhCH2–SCN) were unsuccessful. In the
case of benzyl thiocyanate, we only observed a Pt intermediate with an IR absorption
band at 2100 cm−1 assignable to the NCS group, which indicates coordination of the
thiocyanate. Furthermore, even under vigorous reaction conditions (heating to 80 °C or
prolonged reaction time), only the starting material was recovered after recrystallization.
However, as shown in Eq. 1 in Scheme 7, treatment of [Pt(styrene)(PMe3)2], which was
generated from cis-[PtEt2(PMe3)2] and styrene at 80 °C in toluene, with benzyl
isothiocyanate in a 1:2 molar ratio afforded the S-coordinated dithiocarbonimidato
Pt(II) complex [Pt(S2C=N–CH2Ph)(PMe3)2] (17), in 28% yield.
8

The pathway of the above-mentioned reaction (Eq. 1) is quite similar to that
observed in the reactions of diethyl Pd(II) complexes: π-coordination of R–NCS to the
Pt(0) center and subsequent sulfur abstraction. Interestingly, cis-[PtEt2(PMe3)] reacts
with PhCH2–SCN (benzyl thiocyanate) to give a C–S oxidative addition product, a six-
coordinated Pt(IV) complex (18), as white crystals (Eq. 2). The IR spectrum of complex
18 displays a characteristic NCS stretching band at 2107 cm−1. The solution NMR
spectrum of 18 indicates that the complex exists as a mixture of cis-
[Pt(Et)2(CH2Ph)(NCS)(PMe3)2] (A) and trans-[Pt(Et)2(CH2Ph)(NCS)(PMe3)2] (B) in a
64:34 ratio. The 1H NMR signals for the benzylic (CH2Ph) protons exhibit a doublet of
doublets (JPH = 10, 20 Hz) with a satellite (JPtH = 91 Hz) at δ 3.06 ppm and δ 2.59 ppm
due to the cis form (A) and a triplet (JPH =7.7 Hz) with a satellite (JPtH = 103 Hz) at δ
31
2.55 ppm from the trans form (B). In addition, the P NMR signals show two doublets
(J = 13 Hz) at δ −35.6 and −38.4 ppm with a satellite (JPtP = 1309, 1053 Hz,
respectively) from the cis form (A) and a singlet at δ −39.4 ppm with a satellite (JPtP
=
1118 Hz) from the trans form (B). The structure of complex B, one of isomeric pair,
was determined using X-ray diffraction (Figure 4). Its molecular structure clearly shows
formation of a six-coordinated Pt(IV) complex (B) by oxidative addition of benzyl
thiocyanate. In this reaction, we did not observe reductive elimination to give organic
compounds by C–C homocoupling or C–N or C–S heterocoupling. The results shown in
9

Schemes 4 and 7 can be explained on the basis of the well-known fact that a Pt complex
is more thermally stable than the corresponding Pd complex.
As shown in Schemes 4 and 6, direct reactions of R–SCN with dialkyl Pd(II)
complexes exhibit S–C or R–S bond cleavage depending on the starting materials. In
contrast, similar reactions involving the diethyl Pt(II) complex proceed via trans or cis
oxidative addition of R–SCN to afford the six-coordinated Pt(IV) complexes. The
structures of these Pt(IV) complexes were confirmed by comparing them with those
reported in the literature, which were prepared by trans or cis oxidative addition of alkyl
halides to dialkyl Pt(II) complexes [32–35].
Conclusion
We investigated the reactivity of organic pseudohalides (R–NCS and R–SCN)
toward dialkyl bis(phosphine) complexes of Pd(II) and Pt(II). As expected, the chiral
R–NCS reagents reacted with the Pd(II) complexes to afford S,S-coordinated Pd(II)
complexes containing a dithiocarbonimidato (S2C=N–R) moiety, with retention of the
absolute configuration at the R group. When allyl isothiocyanate used, the cationic η3-
allyl Pd complex [Pd(η3-allyl)(PMe3)2]+(NCS)− was obtained. Treatment of a diethyl
Pd(II) complex with 2 equiv of R–SCN afforded a Pd(II) cyanide complex and an
organic disulfide by selective S–C bond cleavage of R–SCN. In contrast, similar
reactions involving a dimethyl analog afforded different products, [PdMe(NCS)L2] or
[Pd(NCS)2L2] as the major product, depending on the supporting ligand. Treatment of
[Pt(styrene)(PMe3)2] with benzyl isothiocyanate afforded the S-coordinated
dithiocarbonimidato Pt(II) complex, [Pt(S2C=N–CH2Ph)(PMe3)2]. In contrast, the
reaction of cis-[PtEt2(PMe3)2] with benzyl thiocyanate proceeded via trans or cis
oxidative addition of R–SCN to afford a Pt(IV) complex. In conclusion, Pd(II) and
Pt(II) diethyl complexes are more reactive toward organic isothiocyanates or
thiocyanates than the dimethyl analogs are. Furthermore, the reactivites of the Pd(II)
dialkyl complexes toward R–NCS are higher than the Pt(II) analogs. In contrast, similar
reactions involving R–SCN produced different products, depending on the metal center
and the PR3 ligands.
10

Experimental
All manipulations of air-sensitive compounds were performed under N2 or Ar
using Schlenk-line techniques. Solvents were distilled from Na–benzophenone.
Elemental analyses were performed at the analytical laboratories at the Basic Science
Institute of Korea and at Kangnung-Wonju National University. IR spectra were
recorded using a Perkin Elmer BX spectrophotometer. NMR (1H, 13C{1H}, and
31P{1H}) spectra were obtained in CDCl3 using a JEOL Lamda 300 MHz spectrometer.
Chemical shifts were referenced to internal Me4Si and to external 85% H3PO4. X-ray
reflection data were obtained at either the Korea Basic Science Institute (Jeonju Center)
and the Cooperative Center for Research Facilities at Sungkyunkwan University. The
complexes trans-[PdR2L2] (L = PMe3, PEt3, and PMe2Ph) [36] and cis-[PtR2L2] (PMe3
and PEt3) [37] were prepared using the literature method.
Reactions of trans-[PdEt2L2] (L = PMe3, PMe2Ph) with R–NCS (R = benzyl;
CH(CH3)Ph, R-(−); CH(CH3)Ph, S-(+); 1-Indanyl, S-(+))
Benzyl isothiocyanate (258 µl, 1.94 mmol) and THF (3 cm3) were sequentially
added at 0 ºC to a Schlenk flask containing trans-[PdEt2(PMe3)2](0.308 g, 0.97 mmol).
The reaction mixture was stirred at room temperature for 5 h; the initial yellow solution
turned to a pale-orange solution. The solvent was completely removed under vacuum.
The resulting residue was solidified with hexane. The solids were filtered and washed
with n-hexane (2 cm3 × 2) to give crude solids, which were recrystallized from
CH2Cl2/hexane to give cis-[Pd(S2C=N–CH2Ph)(PMe3)2] (1, 0.171 g, 70%) as a pale
yellow solids. IR (KBr/cm−1): 1568 (C=N). 1H NMR: δ 1.52 (d, J = 8.4 Hz, 18H, PCH3),
4.86 (s, 2H, CH2), 7.12–7.18 (m, 1H, Ph), 7.23–7.28 (m, 2H, Ph), 7.39–7.41 (m, 2H, Ph).
131C{1H} NMR: δ 16.2 (ddd, J = 5.0, 14, 25Hz, PCH3), 51.5(s, CH2), 125.9, 127.9,
31
128.2, 141.1, 172.8 (s, C=N). P{1H}NMR: δ 16.9 (dd, J = 53, 87Hz). Anal. Calc. for
C14H25NP2S2Pd: C, 38.23; H, 5.73; N, 3.18. Found: C, 37.75; H, 5.78; N, 3.03.
Complexes cis-[Pd(S2C=N–R)(PMe3)2] (R = CH(CH3)Ph, R-(−), 2), cis-
[Pd(S2C=N–R)(PMe3)2] (R = CH(CH3)Ph, S-(+), 3), cis-[Pd(S2C=N–R)(PMe2Ph)2] (R =
CH(CH3)Ph , R-(-), 4), cis-[Pd(S2C=N–R)(PMe2Ph)2] (R = CH(CH3)Ph, S-(+), 5), cis-
[Pd(S2C=N–R)(PMe3)2] (R = 1-indanyl, S-(+), 6) were prepared analogously.
11

Complex 2 (71%). IR (KBr/cm−1): 1556 (C=N). 1H NMR: δ 1.49 (br, 9H, PCH3),
1.52 (br, 9H, P(CH3)3), 5.46 (q, J = 6.6 Hz, 1H, CH), 7.11–7.16 (m, 1 H, Ph), 7.22–
13
7.27(m, 2H, Ph), 7.45–7.48(m, 2H, Ph). C{1H} NMR: δ 16.2 (ddd, J = 5.6, 17, 25 Hz,
PCH3), 23.9 (s, Me), 55.4 (s, CH), 125.8, 127.0, 127.9, 146.4, 172.0 (s, C=N).
31P{1H}NMR: δ –17.1 (dd, J = 51, 77 Hz). Anal. Calc. for C15H27NP2S2Pd: C, 39.69; H,
5.99; N, 3.08. Found: C, 39.78; H, 5.83; N, 2.91.
Complex 3 (65%). IR (KBr/cm−1): 1567 (C=N). 1H NMR: δ 1.50 (d, 18 H, J = 3.6
Hz, PCH3), 5.46 (q, J = 6.6 Hz, 1H, CH), 7.11–7.16 (m, 1H), 7.23–7.28 (m, 2 H), 7.45–
7.48 (m, 2 H). 13C{1H} NMR: δ 16.4 (ddd, J = 5.6, 18, 25 Hz, PCH3), 24.2 (s, Me), 55.5
31
(s, CH), 126.0, 127.3, 127.6, 146.6, 167.6 (s, C=N). P{1H}NMR: δ –16.5 (dd, J = 51,
76 Hz). Anal. Calc. for C15H27NP2S2Pd: C, 39.69; H, 5.99; N, 3.08. Found: C, 39.88; H,
6.01; N, 2.87.
1
Complex 4 (72%). IR (KBr/cm–1): 1560 (C=N). H NM: δ 1.52 (dd, J = 1.1, 9.5
Hz , 18H, PCH3), 2.11 (m, 1H, CH2), 2.45 (m, 1H, CH2), 2.86 (m, 1H, CH2), 3.04 (m,
1H, CH2), 5.78 (t, J = 7.3 Hz, 1H, CH), 7.08–7.18 (m, 3H, Ar), 7.28–7.34 (m, 1H, Ar).
13C{1H} NMR: δ 16.2 (ddd, JPC = 5.6, 17, 24 Hz, PCH3), 30.9 (CH2), 34.1 (CH2), 61.4
(d, JPC = 1.2 Hz, CH2), 124.0, 125.1, 126.0, 126.4, 143.5, 146.2, 172.0 (s, C=N)
31P{1H}NMR: δ –16.2 (dd, J = 26, 57 Hz). Anal. Calc. for C16H27NP2S2Pd: C, 41.25; H,
5.84; N, 3.01. Found: C, 41.65; H, 5.87; N, 3.06.
1
Complex 5 (73%). IR (KBr/cm−1): 1569 (C=N). H NMR: δ 1.43–1.48 (m, 12H,
PCH3), 1.55 (d, J = 6.6 Hz, 3H, CH3), 5.52 (q, J = 6.6 Hz, 1H, CH) 7.13–7.18 (m, 2 H),
7.25–7.40 (m, 9 H), 7.49–7.52 (m, 4H). 13C{1H} NMR: δ 14.0 (ddd, J = 1.9, 5.6, 25 Hz,
PCH3), 24.1 (s, CH3), 55.4 (s, CH), 125.8, 127.1, 127.9, 128.7 (t, JPC = 1.9 Hz), 128.9 (t,
JPC = 1.9 Hz), 130.6 (ddd, J = 1.9, 5.5, 25 Hz), 148.4, 170.6 (s, C=N). 31P{1H}NMR: δ
–7.70 (dd, J = 48, 64 Hz). Anal. Calc. for C25H31NP2S2Pd: C, 51.95; H, 5.40; N, 2.42.
Found: C, 51.98; H, 5.57; N, 2.12.
1
Complex 6 (76%). IR (KBr/cm−1): 1570 (C=N). H NMR: δ 1.43–1.48 (m, 12H,
PCH3), 1.55 (d, J = 6.6 Hz, 3H, CH3), 5.52 (q, J = 6.6 Hz, 1H, CH) 7.13–7.18 (m),
7.25–7.40 (m), 7.49–7.52 (m). 13C{1H} NMR: δ 14.0 (ddd, JPC = 1.9, 5.6, 25 Hz, PCH3),
24.1 (s, CH3), 55.4 (s, CH), 125.8, 127.1, 127.9, 128.8 (dd, J = 1.9, 8.0 Hz), 130.6 (ddd,
J = 2.5, 7.5, 9.6 Hz), 146.4, 170.5 (s, C=N). 31P{1H}NMR: δ –7.70 (dd, J = 48, 64 Hz).
12

Anal. Calc. for C25H31NP2S2Pd: C, 51.95; H, 5.40; N, 2.42. Found: C, 52.30; H, 5.54; N,
2.14.
Reactions of cis-[Pd(S2C=N–R)(PMe3)2] (R = CH(CH3)Ph, R-(−) or S-(+)) with
depe or dmpe
THF (7 cm3) and depe (60 µl, 0.26 mmol) were added at room temperature to a
Schlenk flask containing 2 (0.117 g, 0.26 mmol). The reaction mixture was stirred for 1
h, and then the solvent was completely removed under vacuum. The resulting residue
was solidified with hexane, filtered, and washed with n-hexane (2 cm3 × 2) to give
crude solids, which were recrystallized from THF/hexane to give white crystals of
[Pd{(R)-(−)-S2C=NC(H)(Me)(Ph)}(depe)] (7, 0.126 g, 96%). IR (KBr/cm−1): 1566
(C=N). 1H NMR: δ 1.12–1.27 (m, 12H, PCH2CH3), 1.49 (d, J = 6.6 Hz, 3H, PCH2CH3),
1.81–1.88 (m, 12H, P(Et)+P(CH2), 5.46 (q, J = 6.6 Hz, 1H, CH), 7.13–7.15 (m, 1H),
7.22–7.27 (m, 2H), 7.48–7.50 (m, 2H). 131C{1H} NMR: δ 8.65 (dd, J = 1.9, 5.6 Hz,
PCH2CH3), 19.3 (m, PCH2), 24.1 (s, CH3), 24.4 (ddd, J = 4.3, 16, 25 Hz), 55.5 (s, CH),
125.4, 127.1, 127.7, 146.7, 172.6 (s, C=N). 31P{1H}NMR: δ 61.9 (s). Anal. Calc. for
C19H33NP2S2Pd: C, 44.92; H, 6.55; N, 2.56. Found: C, 45.33; H, 6.59; N, 2.49.
[Pd{(S)-(+)-S2C=NC(H)(Me)(Ph)}(depe)],
8
and
[Pd{(R)-(−)-
S2C=NC(H)(Me)(Ph)}(depe)], 9 were prepared analogously.
Complex 8 (89%). IR (KBr/cm−1): 1557 (C=N). 1H NMR: δ 1.16–1.28 (m, 12H,
PCH2CH3), 1.50 (d, J = 6.6 Hz, 3H, PCH2CH3), 1.86–1.93 (m, 12H, P(Et)+P(CH2), 5.46
(q, J = 6.6 Hz, 1H, CH), 7.10–7.15 (m, 1H), 7.22–7.27 (m, 2H), 7.48–7.50 (m, 2H).
131C{1H} NMR: δ 8.69 (dd, J = 3.1, 3.4 Hz, PCH2CH3), 19.3 (m, PCH2CH3), 24.1 (ddd,
J = 5.0, 19, 25 Hz), 24.2 (s, CH3), 55.5 (s, CH), 125.7, 127.2, 127.9, 127.8, 146.7, 172.5
31
(s, C=N). P{1H}NMR: δ 61.8 (s). Anal. Calc. for C19H33NP2S2Pd: C, 44.92; H, 6.55;
N, 2.56. Found: C, 45.08; H, 6.65; N, 2.54.
1
Complex 9 (87%). IR (KBr/cm−1): 1550 (C=N). H NMR: δ 1.48 (d, J = 6.6 Hz,
3H, CH3), 1.56 (ddd, J = 4.8, 11 Hz, 12H, PCH3), 1.81 (m, 4H, PCH2), 5.44 (q, J = 6.6
Hz, 1H, CH), 7.11–7.16 (m, 1H), 7.23–7.28 (m, 2H), 7.44–7.47 (m, 2H). 13C{1H}
NMR: δ 14.08 (ddd, J = 1.9, 15, 25 Hz, PCH3), 24.0 (s, CH3), 28.2 (ddd, J = 2.5, 30, 57
Hz), 125.8, 127.2, 1273.8, 146.6, 172.4 (s, C=N). 31P{1H}NMR: δ 36.4 (dd, J = 37, 79
13

Hz). Anal. Calc. for C15H25NP2S2Pd: C, 39.87; H, 5.58; N, 3.09. Found: C, 39.62; H,
5.54; N, 3.05.
Reaction of trans-[PdEt2(PMe3)2] with R–NCS (R = allyl )
Allyl isothiocyanate (267 µl, 2.75 mmol) and THF (5 cm3) were added at 0 °C to
a Schlenk flask containing trans-[PdEt2(PMe3)2] (0.436 g, 1.38 mmol). The reaction
mixture was stirred for 18 h at room temperature, and then the solvent was removed
under vacuum. The resulting residue was solidified with diethyl ether/hexane. The
solids were filtered and washed with n-hexane (2 cm3 × 2) to give crude solids, which
were recrystallized from CH2Cl2/ether to give [Pd(η3-allyl)(PMe3)2]+(NCS)− (10, 0.439
1
g, 85%) as a white solid. IR (KBr/cm−1): 2051 (NCS). H NMR: δ 1.64 (d, J = 8.1 Hz,
18H, PCH3), 3.80 (br, 4H, CH2), 5.55 (q, J = 10 Hz, 1H, CH). 13C{1H} NMR: δ 18.2 (d,
JPC = 26 Hz, PCH3), 30.3 (s, CH2), 69.7 (s, CH), 120.8 (s, NCS). 31P{1H}NMR: δ –19.2
(s). Anal. Calc. for C10H23NP2SPd: C, 33.57; H, 6.48; N, 3.92. Found: C, 33.73; H, 6.65;
N, 3.68.
Reactions of trans-[PdEt2L2] (L = PMe3, PMe2Ph) with R–SCN (R = benzyl or Et )
Benzyl thiocyanate (0.353 g, 2.36 mmol) and THF (4 cm3) were added at 0 °C to
a Schlenk flask containing trans-[PdEt2(PMe3)2] (0.375 g, 1.18 mmol). The reaction
mixture was stirred for 18 h at room temperature, and then the solvent was completely
removed under vacuum. The resulting oily residue was solidified with diethyl ether. The
solids were filtered and washed with n-hexane (2 cm3 × 2) to give crude solids, which
were recrystallized from CH2Cl2/ether to give [Pd(CN)2(PMe3)2] (11, 0.169 g, 67%) as a
1
white solid. IR (KBr/cm−1): 2123 (CN). H NMR: δ 1.70 (t, J = 3.8 Hz, 18H, PCH3).
13C{1H} NMR: δ 16.4 (t, JPC = 17 Hz, PCH3), 131.3 (t, JPC = 17 Hz, CN).
31P{1H}NMR: δ −12.3 (s). Complex 11 was identified with the literature data [12d]. The
collected solution was purified by silica gel column (diethyl ether/hexane : 10:1) to
yield a pure PhCH2SSCH2Ph (64%) which was identified by IR, NMR (1H and 13C)
spectroscopy and GC-MS on the basis of literature data [38].
Analogous reactions of trans-[PdR2L2] (L = PMe3, PMe2Ph)2 with benzyl or ethyl
isothiocyanate yielded [Pd(CN)2L2] and ethyl or benzyl disulfide; EtS–SEt (64%) or
14

PhCH2S–SCH2Ph (67%). The final products were characterized using IR and NMR (1H
1
and 13C) spectroscopies and GC–MS. PhCH2S–SCH2Ph: H NMR (CDCl3): δ 3.58 (s,
4H, CH2), 7.20–7.33 (m, 10H, Ph). 13C{1H} NMR: δ 43.2 (s, CH2), 127.3, 128.4, 129.3,
137.24. MS (M+): 246.1.
1
Complex 12 (94%): IR (KBr/cm−1): 2126 (CN). H NMR: δ 1.94 (s, 12H, PCH3),
7.39–7.41 (m, 6H, Ph), 7.66 (m, 4H, Ph). 13C{1H} NMR: δ 16.1 (t, J = 17.1 Hz, PCH3),
128.1 (dd, JPC = 5.0 Hz, Ph), 129.9, 130.0, 130.1. 31P{1H} NMR: δ −5.11 (s).
Reaction of trans-[PdEt2(PMe3)2] with benzyl mercaptan
Benzyl mercaptan (298 µl, 2.52 mmol) and THF (4 cm3) were added at 0 °C to a
Schlenk flask containing trans-[PdEt2(PMe3)2] (0.400 g, 1.26 mmol). The reaction
mixture was stirred for 5 h at room temperature, and then the solvent was completely
removed under vacuum. The resulting residue was solidified with diethyl ether/hexane.
The solids were filtered and washed with n-hexane (2 cm3 × 2) to give crude solids,
which were recrystallized from CH2Cl2/hexane to give yellow crystals of 13 (0.119 g,
1
19%). H NMR: δ 1.42 (br, 18H, PCH3), 3.54 (s, 4H, S–CH2), 7.12–7.18 (m, 2H, Ph),
7.23–7.28 (m, 4H, Ph), 7.35–7.38 (m, 4H, Ph). 13C{1H} NMR: δ 13.8 (t, J = 16 Hz,
PCH3), 35.8 (s, S–CH2–CH3), 125.8, 128.3, 128.4, 145.1. 31P{1H} NMR: δ −15.5 (s).
Anal. Calc. for C20H33P2S2Pd: C, 47.57; H, 6.39. Found: C, 47.53; H, 6.68.
Reactions of trans-[PdMe2L2] (L = PEt3, PMe3) with R–SCN (R = benzyl)
Benzyl thiocyanate (0.278 g, 1.86 mmol) and THF (3 cm3) were added at 0 °C to
a Schlenk flask containing trans-[PdMe2(PEt3)2] (0.347 g, 0.93 mmol). The reaction
mixture was stirred for 18 h at room temperature, and then the solvent was removed.
The resulting oily residue was solidified with diethyl ether/hexane. The solids were
filtered and washed with n-hexane (2 cm3 × 2) to give crude solids, which were
crystallized from excess diethyl ether to give white crystals of 14 (0.193 g, 50%). IR
(KBr/cm−1): 2095 (NCS). 1H NMR: δ −0.05 (br, 3H, PdCH3), 1.14 (q, J = 8.4 Hz, 18 H,
PCH2CH3), 1.73 (br, 12H, PCH2CH3). 13C{1H} NMR: δ −12.0 (br, PdCH3), 8.26 (s,
PCH2CH3), 14.5 (t, J = 13 Hz, PCH2CH3), 135.0 (br, N=C=S).31P{1H} NMR: δ 18.0 (s).
Anal. Calc. for C14H33NP2SPd: C, 40.44; H, 8.00; N, 3.37. Found: C, 40.47; H, 8.35; N,
3.21. The organic products were identified using GLC and GC-MS.
15

The analogous reaction of trans-[PdMe2(PMe3)2] with benzyl thiocyanate
produced a mixture of trans-[Pd(NCS)2(PMe3)2] (15, 33%) as the major product and
trans-[PdMe(NCS)(PMe3)2] (16, below 1%) as minor product. The organic products
1
were analyzed using GC–MS. Complex 15: IR (KBr/cm−1): 2091 (NCS). H NMR: δ
13
1.41 (t, J = 3.3 Hz, 18 H, PCH3). C{1H} NMR: δ 13.8 (t, JPC = 15 Hz, PCH3), 134.5
(br, N=C=S). 31P{1H} NMR: δ −14.0 (s).
Complex 16: 1H NMR: δ −0.19 (t, JPH = 6.9 Hz, 3H, PdCH3), 1.49 (t, J = 3.3 Hz,
18 H, PCH3). 13C{1H} NMR: δ −9.85(br, PdCH3), 15.4 (t, JPC = 15 Hz, PCH3), 133.1 (br,
N=C=S). 31P{1H} NMR: δ −12.4.0 (s).
Reaction of cis-[PtEt2(PMe3)2] with R–NCS (R = benzyl)
Styrene (89 µL, 0.78 mmol) and toluene (3 mL) were added at room temperature
to a Schlenk flask containing cis-[PtEt2(PMe3)2] (0.157 g, 0.39 mmol). The mixture was
heated at 80 °C for 5 h to give a pale-yellow solution. On addition of benzyl
isothiocyanate (103 µL, 0.78 mmol) to the mixture at room temperature, the yellow
solution was transformed to a yellow suspension. The mixture was stirred for 3 h, the
solvent was removed under vacuum, and the resulting residue was solidified with
hexane and CH2Cl2 and stored at −35 °C. The precipitates were filtered and washed
with hexane (2 mL × 2) to obtain the crude solids. Recrystallization from THF/diethyl
ether afforded white crystals of cis-[Pt(S2C=N–CH2Ph)(PMe3)2] (17, 0.058 g, 28%). IR
(KBr/cm−1): 1573 (C=N). 1H NMR: δ 1.64 (dd, J = 2.4, 4.8 Hz, JPtH = 16 Hz, 18H,
PCH3), 4.84 (s, 2H, CH2), 7.15–7.17 (m, 1H, Ph), 7.25–7.28 (m, 2H, Ph), 7.38–7.39 (m,
2H, Ph). 131C{1H} NMR: δ 16.6 (m, PCH3), 51.9(s, CH2), 128.0, 128.5, 128.6, 141.0,
170.6 (d, JPC = 3.5 Hz, C=N). 31P{1H}NMR: δ −29.2 (dd, J = 6.5, 13 Hz, JPtP = 1441
Hz). Anal. Calc. for C14H25NP2S2Pt: C, 31.82; H, 4.77; N, 2.65. Found: C, 31.77; H,
4.97; N, 2.11.
Reaction of cis-[PtEt2(PMe3)2] with R–SCN (R = benzyl)
Benzyl thiocyanate (0.334 g, 2.24 mmol) was added at room temperature to a
THF (3 cm3) solution containing cis-[PtEt2(PMe3)2] (0.454 g, 1.12 mmol). The reaction
mixture was stirred for 18 h at room temperature, and then the solvent was removed
under vacuum. The resulting oily residue was solidified with diethyl ether/hexane. The
16

solids were filtered and washed with n-hexane (2 cm3 × 2) to give crude solids, which
were recrystallized from CH2Cl2/hexane to give white crystals of 18 (0.298 g, 48%).
1
cis-[Pt(Et)2(CH2Ph)(NCS)(PMe3)2] (18A): H NMR: δ 0.80 (dd, J = 5.1 Hz, overlap,
PtCH2CH3), 0.97–1.22 (m, PtCH2), 1.51 (dd, JPH = 5.0, 8.9 Hz, JPtH = overlap, 18H,
PCH3), 2.59 (dd, J = 10, 20 Hz, JPtH = 91 Hz, CH2), 7.14–7.18 (m, 5 H). 13C{1H} NMR:
δ −0.94 (s, JPC = 653 Hz, PCH2CH3), 7.6 (s, JPtC = 651 Hz, PtCH2CH3), 20.3 (ddd, JPC
6.9, 73, 108 Hz, JPtC = 1985 Hz, PCH3). 31P{1H} NMR: δ −35.6 (d, J = 13 Hz, JPtP
1315 Hz), 38.4(d, J = 13 Hz, JPtP = 1065 Hz)
=
=
1
trans-[Pt(Et)2(CH2Ph)(NCS)(PMe3)2] (18B): IR (KBr/cm−1): 2107 (NCS). H
NMR: δ 0.71 (t, JPH = 75, JPtH = 61 Hz, 6H, PtCH2CH3), 0.97–1.22 (m, overlap, PtCH2),
1.41 (d, JPH = 8.5 Hz, JPtH = 8.5 Hz, PCH3), 2.55 (t, J = 7.8 Hz, JPtH = 103 Hz, CH2),
13
7.14–7.18 (m, 5 H). C{1H} NMR: δ −0.94 (s, JPC = 653 Hz, PCH2CH3), 7.6 (s, JPtC
=
651 Hz, PtCH2CH3), 23.9 (dd, JPC = 3.5, 40 Hz, PCH3). 31P{1H} NMR: δ −39.4 (s, JPtP
= 1122 Hz). Anal. Calc. for C18H35NP2SPt: C, 38.98; H, 6.36; N, 2.53. Found: C, 38.99;
H, 6.53; N, 2.24.
X-ray structure determination. Single crystals of 7, 8, 13 and 18B for X-ray
crystallography were grown from THF/n-hexane or CH2Cl2/ n-hexane at −35 °C. X-ray
data were collected using a Siemens P4 or a Bruker Smart APEX diffractometer
equipped with a Mo X-ray tube. All calculations were carried out using SHELXTL
programs [39]. All structures were solved by direct methods. Unless otherwise stated,
all non-hydrogen atoms were refined anisotropically. All hydrogen atoms were
generated in ideal positions and refined in a riding mode.
Details of crystal data, intensity collection, and refinement details are given in
Table 1.
Appendix A. Supplementary material
CCDC Nos. 1004233, 1004234, 1004236, and 1004237 contain the supplementary
crystallographic data for compounds 7, 8, 13, and 18B. These data can be obtained free
of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44
1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk
17

Acknowledgment. This work was supported by the Basic Science Research
Program through the National Research Foundation of Korea (NRF) funded by the
Ministry of Education, Science and Technology (Grant No. 2012R1A1B3001569).
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(b) T. Yoshida, T. Matsuda, S. Otsuka, Inorg. Synth. 28 (1990) 122.
[38] The Aldrich library of 13C and 1H NMR spectra, Aldrich Chemical Company. Vol.
2, 445A.
[39] G. M. Sheldrick, SHELX-97, University of Gőttingen, Germany, 1997.
[40] L. J. Farrugia, ORTEP-3 for Windows, University of Glasgow, 1997.
20

Table 1. X-ray data collection and structure refinements.
complex
7
8
13
18B
formula
C19H33NP2PdS2
507.92
C19H33NP2PdS2
507.92
C20H32P2PdS2
504.92
293(2)
C18H35NP2PtS
554.56
fw
temperature, K
crystal size (mm)
crystal system
space group
a, Å
200(2)
200(2)
296(2)
0.12×0.11×0.08 0.25×0.19×0.07
0.80×0.22×0.18 0.40×0.38×0.34
monoclinic
P21
monoclinic
P21
orthorhombic
Pca21
orthorhombic
Pbca
10.9697(4)
13.1747(5)
15.8585(6)
90
10.939(4)
13.168(5)
15.830(5)
90
17.9262(5)
5.9010(1)
22.4934(6)
90
15.8972(2)
15.2317(2)
18.7656(3)
90
b, Å
c, Å
α, deg
β, deg
95.422(1)
90
95.203(7)
90
90
90
γ, deg
90
90
V, Å3
2281.66(15)
4
2270.7(13)
4
2379.4(1)
4
4543.9(1)
8
Z
dcal, g cm−3
µ, mm−1
1.479
1.486
1.409
1.621
1.140
1.145
1.092
6.409
F(000)
1048
1048
1040
2192
Tmin
0.8753
0.9143
2.01–28.30
16617
9060
0.7627
0.9241
1.29–26.21
13495
7900
0.4755
0.8277
1.81–28.33
28249
5255
0.1186
0.2670
2.15–28.45
66050
5702
Tmax
θ range (º)
No. of reflns Measured
No. of reflns Unique
No. of reflns with I > 2σ(I)
No. of params Refined
Max., in ∆ρ (e Å-3)
Min., in ∆ρ (e Å-3)
6861
6694
3793
4396
451
451
227
208
0.925
0.851
0.520
1.472
−0.688
−0.557
0.00(3)
0.985
−0.266
0.53(4)
0.993
−0.629
Absolute structure parameter −0.01(2)
GOF on F2
R1a
wR2b
0.947
1.059
0.0336
0.0538
0.0412
0.0321
0.0595
0.0249
0.0582
0.0838
a
b
2
R = Σ[|Fo| Fc|]/Σ|Fo|], wR2 = {Σ[w(Fo2 − Fc2)2]/Σ[w(Fo )2]}1/2
− |
21

Figure 1. ORTEP drawing [40] of 7 showing the atom-labelling scheme and 50%
probability thermal ellipsoids. Selected bond lengths (Å) and angles (°): Pd1–P1
2.246(1), Pd1–P2 2.247(1), Pd1–S2 2.320(1), Pd–S1 2.337(1), N1-C11 1.246(5); P1–
Pd1–P2 86.40(5), P1–Pd1)–S2 96.81(4), P2–Pd1–S1 100.47(5), S2–Pd1–S1 76.66(4).
22

Figure 2. ORTEP drawing of 8. Selected bond lengths (Å) and angles (°): Pd1–P1
2.244(2), Pd1–P2 2.249(2), Pd1–S2 2.321(2), Pd1–S1 2.330(2), N1–C11 1.263(7); P1–
Pd1–P2 86.36(6), P1–Pd1–S2 96.78(6), P2–Pd1–S2 174.76(7), S2–Pd1–S1 76.69(6).
23

Figure 3. ORTEP drawing of 13. Selected bond lengths (Å) and angles (°): Pd1–P2
2.314(1), Pd1–P1 2.315(1), Pd1–S2 2.347(1), Pd1–S1 2.347(1), S1–C1 1.827(5), S2–C8
1.836(4); P2–Pd1–P1 179.73(7), P2–Pd1–S2 86.64(5), P1–Pd1–S2 93.43(4), S2–Pd1–
S1,179.15(5), C1–S1–Pd1 99.84(16), C8–S2–Pd1 100.4(2).
24

Figure 4. ORTEP drawing of 18B. Selected bond lengths (Å) and angles (°): Pt1–C1
2.100(4), Pt1–C16 2.112(4), Pt1–N1 2.113(4), Pt1–C14 2.125(4), Pt1–P2 2.392(1), Pt1–
P1 2.393(1), S1–C18 1.624(4), N1–C18 1.146(5); C1–Pt1–C16 91.7(2), C1–Pt1–N1
176.0(1), C16–Pt1–C14 85.1(2), N1–Pt1–P2 89.3(1), C16–Pt1–P1 173.2(2), P2–Pt1–P1
95.44(4), C18–N1–Pt1 169.2(4), N1–C18–S1 179.0(4).
25

Graphical Abstract
Reactivities of organic isothiocyanates and thiocyanates toward dialkyl
bis(phosphine) complexes of palladium(II) and platinum(II)
Seon Gye Lee, Keun-Young Choi, Yong-Joo Kim*, SuJin Park, Soon W. Lee
26

Graphical Abstract
Reactivities of organic isothiocyanates and thiocyanates toward dialkyl
bis(phosphine) complexes of palladium(II) and platinum(II)
Seon Gye Lee, Keun-Young Choi, Yong-Joo Kim*, SuJin Park, Soon W. Lee
Organic isothiocyanates (R–NCS) reacted with trans-[PdEt2(PR3)2] to afford S,S-
coordinated dithiocarbonimidato complexes [Pd(S2C=N–R)L2]. When allyl
isothiocyanates was used, the cationic η3-allyl Pd complex [Pd(η3-allyl)
(PMe3)2]+(NCS)− was formed. In contrast, organic thiocyanates (R–SCN) underwent
selective S–C oxidative addition to trans-[PdEt2L2] to afford [Pd(CN)2L2] and RS–SR.
Interestingly, benzyl thiocyanate was oxidatively added to cis-[PtEt2(PMe3)2] to afford a
mixture of two octahedral Pt(IV) complexes.
27