Reactivity of di(azido)bis(phosphine) complexes of Ni(II), Pd(II) and Pt(II) toward organic isothiocyanates: Synthesis, structures, and properties of bis(tetrazole-thiolato) and bis(isothiocyanato) complexes

Article abstract of DOI:10.1039/b305341p

Di(azido)bis(phosphine) complexes of Group 10 metals {M(N₃)₂(PR₃)₂} underwent substitution with trimethylsilyl isothiocyanate (Me₃Si-NCS) to give the corresponding bis(isothiocyanato) complexes, M(NCS)₂L₂ (M = Pd, L = PMe₃ (1), PEt₃ (2), PMe₂Ph (3); M = Ni, L = PMe₃ (4); M = Pt, L = PEt₃ (5)), in which the isothiocyanato ligand is N-bound to the metal. By contrast, the bis(azido) complexes of Pd(II) and Pt(II) underwent 1,3-cycloaddition with organic isothiocyanates (R-NCS) to give tetrazole-containing thiolato complexes, M{S[CN₄(R)]}₂L₂ (M = Pd, L = PMe₃, R = allyl (6), benzyl (7), ethyl (8), phenyl (9), 2,6-dimethylphenyl (10); L = PMe₂Ph, R = phenyl (11); L = PEt₃, R = 2,6-dimethylphenyl (12); M = Pt, L = PMe₃, R = Ph (13), Et (14); L = PEt₃, R = Ph (15)). The chelating phosphine analogues, M{S[CN₄(R)]}₂L₂ (L-L = depe (1,2-bis(diethylphosphino)ethane): R = Ph, M = Pd (16), Pt (17); R = 2,6-dimethylphenyl, M = Pt (18)) could also be obtained. Molecular structures of 6, 9, 14 and 18 clearly show the S-coordination of the thiolato ligands in these complexes. Treatments of tetrazole-thiolate complexes with benzoyl halide derivatives afforded various organic sulfides.

Full text of DOI:10.1039/b305341p

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Reactivity of di(azido)bis(phosphine) complexes of Ni(II), Pd(II)
and Pt(II) toward organic isothiocyanates: synthesis, structures,
and properties of bis(tetrazole-thiolato) and bis(isothiocyanato)
complexes
Yong-Joo Kim,*a Jin-Taek Han,a Seok Kang,a Won Seok Hanb and Soon W. Leeb
a Department of Chemistry, Kangnung National University, Kangnung 210-702, Korea.
E-mail: yjkim@knusun.kangnung.ac.kr
b Department of Chemistry, Sungkyunkwan University, Natural Science Campus,
Suwon 440-746, Korea
Received 12th May 2003, Accepted 17th July 2003
First published as an Advance Article on the web 28th July 2003
Di(azido)bis(phosphine) complexes of Group 10 metals {M(N3)2(PR3)2} underwent substitution with trimethylsilyl
isothiocyanate (Me3Si–NCS) to give the corresponding bis(isothiocyanato) complexes, M(NCS)2L2 (M = Pd,
L = PMe3 (1), PEt3 (2), PMe2Ph (3); M = Ni, L = PMe3 (4); M = Pt, L = PEt3 (5)), in which the isothiocyanato ligand
is N-bound to the metal. By contrast, the bis(azido) complexes of Pd() and Pt() underwent 1,3-cycloaddition with
organic isothiocyanates (R–NCS) to give tetrazole-containing thiolato complexes, M{S[CN4(R)]}2L2 (M = Pd,
L = PMe3, R = allyl (6), benzyl (7), ethyl (8), phenyl (9), 2,6-dimethylphenyl (10); L = PMe2Ph, R = phenyl (11);
L = PEt3, R = 2,6-dimethylphenyl (12); M = Pt, L = PMe3, R = Ph (13), Et (14); L = PEt3, R = Ph (15)). The chelating
phosphine analogues, M{S[CN4(R)]}2L2 (L–L = depe (1,2-bis(diethylphosphino)ethane): R = Ph, M = Pd (16),
Pt (17); R = 2,6-dimethylphenyl, M = Pt (18)) could also be obtained. Molecular structures of 6, 9, 14 and 18 clearly
show the S-coordination of the thiolato ligands in these complexes. Treatments of tetrazole-thiolate complexes with
benzoyl halide derivatives afforded various organic sulfides
tetrazole-containing thiolato complexes or isothiocyanato
Introduction
complexes, depending upon the nature of organic isothio-
Metal–azido complexes have been an interesting subject for
cyanates (Scheme 1).
many decades due to their analogous behavior to those of
organic azides, including cycloaddition with dipolar nucleo-
philes or electrophiles and thermal or photo-initiated decom-
position to metal nitrides or cluster compounds.1 Various
unsaturated reagents (such as nitriles, alkynes and isocyanides)
undergo cycloaddition reactions to the coordinated azido
ligand to give a variety of heterocycles.2–13 In particular, organic
isothiocyanates (R–NCS) are well known useful reagents for
heterocycle formation by dipolar cycloaddition or electrophilic
Scheme 1
addition.
Herein, we report the synthesis and structures of tetrazole-
containing thiolato complexes of Pd() and Pt() as well as
isothiocyanato complexes of the Group 10 metal triad. We also
report the reactivity of these complexes toward electrophiles,
Recently, we have reported the cycloaddition reaction of
azido or di(azido)bis(phosphine) complexes of Ni(), Pd() and
Pt() with various organic isocyanides.14 We have also reported
that those reactions give complexes containing C-coordinated
(five-membered) tetrazolato rings or carbodiimido (N᎐C᎐N)
leading to the formation of organic sulfides. Our synthetic
᎐ ᎐
strategy for preparing metal–iosthiocyanato complexes is
expected to apply to the preparation of other metal complexes,
and it may be an alternative to the known metathesis reaction
that requires relatively vigorous conditions.
groups by dipolar cycloaddition, depending upon the nature of
the isocyanide. These results prompted us to extend our scope
of the dipolar cycloaddition of organic isothiocyanates into
the azido ligand, leading to the formation of heterocycles.
Although several studies regarding the dipolar cycloaddition of
organic isothiocyanates into the azido ligand have been carried
out,3,8,12,15,16 the formation of thiolato complexes containing a
tetrazole ring, which has a direct metal–sulfur bond, has not
been reported. Even in organic chemistry, the number of cases
for the formation of tetrazole-containing thiolato (or tetra-
zolethiolate) compounds is quite limited.17
Beck et al. previously prepared anionic Pd() and Pt() as
well as neutral Au(), Cu(), Ag() and Hg() thiolato
complexes containing tetrazole rings by the metathesis of metal
halides with alkali metal salts of tetrazole mercaptan or by the
reactions of metal halides with alkyl mercaptans in the presence
of amine.18 Recently, Nöth et al. reported several crystal
structures of the above tetrazole–thiolato complexes.19 In this
work, we have found that di(azido)bis(phosphine) complexes
of Group 10 metals react with organic isothiocyanates to give
Results and discussion
Reactions of di(azido)bis(phosphine) complexes of Ni(II), Pd(II)
and Pt(II) with organic isothiocyanates
Treating di(azido)–Pd(), –Ni() and –Pt() complexes with
two equivalents of trimethylsilyl isothiocyanate (Me3Si–NCS)
gave the corresponding bis(isothiocyanato) complexes,
M(NCS)2L2, in high yields (eqn. (1)).
These reactions proceed smoothly at room temperature.
Isolated complexes 1–5 have been characterized by IR, NMR,
and elemental analyses. IR spectra of these complexes show
strong absorption bands at 2077–2098 cmϪ1 due to the N᎐C᎐S
᎐ ᎐
group, which is shifted to a higher wavenumber compared with
ν(N3) at ca. 2030 cmϪ1 of the starting material. The values are
similar to those reported for other isothiocynato complexes.20
T h i s j o u r n a l i s © T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 3
D a l t o n T r a n s . , 2 0 0 3 , 3 3 5 7 – 3 3 6 4
3357

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(1)
(3)
13C{1H} NMR spectra display a signal at ca. 130 ppm corre-
sponding to the carbon atom of the NCS group. 31P NMR
spectra exhibit the presence of geometric isomers of trans- and
cis-M(NCS)2L2, depending upon the metal or ligand. Also, the
amount of Me3SiN3 formed was identified by GC and com-
pared with a genuine sample. The isothiocyanato complexes are
generally obtained by the metathesis of metal halides with
KSCN in alcoholic or aqueous media. However, those meta-
thesis reactions frequently give various linkage isomers such as
S-coordinated or S,N-mixed coordinated complexes including
geometrical siomers. In contrast, our reactions smoothly
proceed in organic solvents and undesirable linkage isomers
such as M(NCS)(SCN)L2 and M(SCN)2L2 are not formed.21–24
To our best knowledge, there is only one example of intro-
duction of an isothiocyanato group into Rh complexes using
trimethylsilyl isothiocyanate in organic solvents.25 Therefore,
our synthetic method seems to be a relatively simple and
straightforward tool to introduce the isothiocyanato group into
transition-metal complexes without forming undesirable link-
age isomers. We have carried out similar reactions of di(azido)-
bis(phosphine) complexes of Pd() and Pt() with organic
isothiocyanates possessing allyl, benzyl, ethyl, phenyl or 2,6-
dimethylphenyl groups. Interestingly, these reactions gave tetra-
zole-containing thiolato complexes, cycloaddition products
rather than substitution products (eqn. (2)).
The formation of bis(tetrazole-thiolato) complexes was easily
monitored by the IR spectra. IR spectra of the products do not
show any characteristic bands at 2000–2100 cmϪ1 due to the
ν(N ) of starting materials or ν(N᎐C᎐S) of possible products,
᎐ ᎐
3
suggesting no replacement of N3 with NCS. 13C NMR spectra
of all the products display a singlet at 157–161 ppm due to the
carbon atom on the tetrazolato ring (CN4) bonded to sulfur.
In addition, one signal in the 31P{1H} NMR spectra of the
complexes strongly support the absence of geometrical isomers.
Of course, the definitive evidence for the connectivity of atoms
in products has been obtained from crystallographic studies
of some (complexes 6,9,14 and 18) of these thiolato com-
plexes. Tables 1 and 2 show the analytical and NMR data of the
thiolato complexes 6–18.
Several research groups independently reported that Pd– and
Ni–azido complexes reacted with phenyl (or methyl) iso-
thiocyanate to give N-coordinated tetrazolato complexes by
1,3-cycloaddition of the isothiocynate into the metal–azido
bond.3,8,12,15,16 However, the formation of S-coordinated thio-
lato compounds from metal–azido complexes and organic
isothiocyanates by the dipolar cycloaddition of isothiocynates
to the coordinated azido bond has not been reported yet. In this
work, we did not observe the formation of N-coordinated
tetrazolato complexes as well as other N-bonded isomers
(eqn. (4)). Instead, we have confirmed tetrazole-thiolato com-
plexes to be a sole product in the reactions of di(azido)–Pd()
and –Pt() complexes with organic isothiocyanates.
(4)
Structures
Molecular structures of 4–6, 9, 14 and 18 have been determined
by X-ray crystallography. The crystal data and intensity data
are given in Table 3. Figs. 1 and 2 show ORTEP drawings of
4 and 5, which have trans- or cis-oriented square-planar
geometry depending on the coordinated phosphine ligands.
These ORTEP drawings clearly show the N-coordination of
isothiocyanato ligands (NCS). The bond lengths of Ni–N
(1.834(2) Å) in 4 and Pt–N (2.06(1) Å) in 5 are close to those in
other terminal isothiocyanato complexes, Ni(NCS)2(PPh2Me)2
(1.802(4) Å),24 Ni(NCS)2(PPh3)2 (1.819(3) Å),26 and [Pt(NCS)-
(2)
Di(azido)–Pd complexes smoothly react with organic iso-
thiocyanates at room temperature to give the corresponding
thiolato complexes. In contrast, the corresponding reaction of
di(azido)–Pt() complexes at room temperature do not go to
completion. However, the reactions at 60 ЊC for 5 h give a com-
plete conversion to the bis(thiolato) complexes. Unfortunately,
the yellow reaction product from Ni(N3)2(PMe3)2 and two
equivalents of 2,6-dimethylphenyl isothiocyanate at room
temperature strongly resists characterization because of its
extremely poor solubility in organic solvents. In the cases of
other organic isothiocyanates, we could identify the presence of
the NCS group, presumably arising from the cleavage of the
tetrazolato ring or the replacement of N3 with the NCS group.
Similar reactions of di(azido)–Pd() and –Pt() complexes con-
taining chelating phosphines with organic isothiocynates also
produced the corresponding bis(thiolato) complexes (eqn. (3)),
but require longer reaction times or heating conditions (60 ЊC).
(PEt ) ] (p-C H –(C᎐C) ) (2.024(9) Å).27 As in the vast majority
᎐
᎐
3
2 2
6
4
2
of other isothiocyanato complexes, complexes 4 and 5 have an
essentially linear N᎐C᎐S ligand (179.4(2)Њ in 4 and 178(1)Њ in 5).
᎐ ᎐
On the basis of the crystallographic data and 31P NMR spectra
of the complexes, we can rule out the possibility of the
formation of other linkage isomers such as S-coordinated
M(SCN)2L2 or mixed coordinated M(SCN)(NCS)L2 complexes
both in solution and in the solid state.
Figs. 3–6 show the molecular structures of complexes 6, 9, 14
and 18, respectively. The ORTEP drawings of these complexes
clearly show the square-planar coordination, which has two
phosphine and two thiolato ligands possessing a five-membered
D a l t o n T r a n s . , 2 0 0 3 , 3 3 5 7 – 3 3 6 4
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Table 1 Colors, yields and analytical data for tetrazole-thiolato complexes 6–18
Analysesa (%)
C
Complex
Color
Yield (%)
H
N
6, Pd(SCN4R)2(PMe3)2
(R = allyl)
7, Pd(SCN4R)2(PMe3)2
(R = CH2Ph)
8, Pd(SCN4R)2(PMe3)2
(R = Et)
9, Pd(SCN4R)2(PMe3)2
(R = Ph)
10, Pd(SCN4R)2(PMe3)2
(R = 2,6-Me2C6H3)
11, Pd(SCN4R)2(PMe2Ph)2
(R = Ph)
12, Pd(SCN4R)2(PEt3)2
(R = 2,6-Me2C6H3)
13, Pt(SCN4R)2(PMe3)2
(R = Ph)
14, Pt(SCN4R)2(PMe3)2
(R = Et)
15, Pt(SCN4R)2(PEt3)2
(R = Ph)
Yellow
Yellow
Yellow
Yellow
Yellow
Yellow
Yellow
White
White
White
White
White
White
75
81
88
59
45
93
72
92
91
64
76
66
92
31.39
(31.09)
41.24
(41.22)
27.82
(27.88)
39.25
(39.19)
43.27
(43.08)
48.35
(48.88)
48.01
(47.84)
33.93
(34.24)
23.82
(23.80)
39.70
(39.74)
43.08
(43.21)
38.37
(38.14)
39.88
5.31
(5.22)
5.05
(5.03)
5.46
(5.46)
4.62
(4.60)
5.52
(5.42)
4.38
(4.38)
6.47
(6.42)
4.02
(4.02)
4.67
(4.66)
5.21
(5.13)
5.29
(5.14)
4.65
21.02
(20.72)
17.50
(17.48)
21.34
(21.68)
18.50
(18.28)
16.95
(16.75)
15.03
(15.20)
14.90
(14.88)
15.63
(15.97)
18.51
(18.5)
13.95
(14.26)
16.29
(16.80)
14.58
16, Pd(SCN4R)2(depe)
(R = Ph)
17, Pt(SCN4R)2(depe)
(R = Ph)
18, Pt(SCN4R)2(depe)ؒ2H2O
(R = 2,6-Me2C6H3)
(4.53)
5.04
(5.47)
(14.83)
12.39
(13.22)
(39.66)
a Calculated values are given in parentheses.
Fig. 1 ORTEP drawing34 of 4 showing the atom-labeling scheme and
50% probability thermal ellipsoids. Selected bond lengths (Å) and
angles (Њ): Ni1–N1 1.834(2), Ni1–P1 2.2287(6), S1–C1 1.621(2), N1–C1
1.157(3); N1–Ni1–P1 90.98(6), C1–N1–Ni1 176.07(19), N1–C1–S1
179.4(2).
Fig. 2 ORTEP drawing of 5 showing the atom-labeling scheme and
50% probability thermal ellipsoids. Selected bond lengths (Å) and
angles (Њ): Pt1–N(1) 2.06(1), Pt1–P1 2.263(3), S1–C5 1.61(1), N1–C5
1.14(1); N1#1–Pt1–N1 87.1(6), N1–Pt1–P1 171.4(3), N1–Pt1–P1#1
84.3(3), P1–Pt1–P1#1 104.4(2), N1–C5–S1 178(1).
(2-substituted) tetrazole ring. The two tetrazole rings (CN4) in
Figs. 3–5 are mutually trans and oriented perpendicular to the
molecular plane, probably to minimize steric repulsion between
two phosphines and the two alkyl groups attached to the tetra-
zole rings. The equatorial plane in Fig. 3, defined by two P, two
S, and Pd atoms is almost planar with an average atomic
displacement of 0.0063 Å, and the Pd metal lies on the crystal-
lographic center of symmetry.
2Ϫ
Pd(SCN4Me)4 (2.332(1) and 2.339(1) Å), neutral Au(SCN4-
Me)(PPh3) (2.325(1) Å) and Au(SCN4Ph)(PPh3) (2.304(2) Å).
However, these bond lengths are much shorter than those in
Ag (2.530(1) Å) or Hg (2.566(3) Å)19 tetrazole-thiolates. The
M–S–C bond angle (100.14(9)Њ) of 6 is smaller than those of
9 (105.3(10)Њ), 14 (102.2(2)Њ) and 18 (102.3(4)Њ), suggesting
higher steric hindrance of the 2-allyl group on the tetrazolato
ring than those of other 2-substitutents, and these M–S–C
bond angles fall in the range (97.5–106.9Њ) as found for other
neutral tetrazole-thiolatates.19
Recently, Nöth et al.19 reported several crystal structures of
neutral and anionic tetrazole-thiolate complexes of transition
metals. However, for Group 10 metals, there has been only one
anionic tetrazole-thiolate complex, Pd(SCN4Me)42Ϫ, and the
corresponding neutral complexes have not been reported. The
Pd–S bond lengths {2.342(7) Å for 6 and 2.325(8) Å for 9} and
Pt–S bond lengths {2.337(1) Å for 14 and 2.365(3) Å for 18} are
close to those for other tetrazole-thiolato complexes: anionic
Chemical properties
We have examined the reactivity of tetrazole-thiolate complexes
toward several electrophiles to gain insight into their chemical
properties and potential applications to organic synthesis.
D a l t o n T r a n s . , 2 0 0 3 , 3 3 5 7 – 3 3 6 4
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Table 2 NMR data (δ, J/Hz) of tetrazole-thiolato complexes 6–18
1H NMRa
Complex
PR3 (R = Me, Et)
1.35 (t, 18H, J = 4)
Others
13C{1H}b
31P{1H}c
6
4.93 (dt, 4H, J = 1.6, 3, CH2)
5.25 (dd, 4H, J = 0.9, 1, CH2)
6.00 (m, 2H, CH)
13.3 (t, J = 16, CH3)
49.2, 119.5, 130.5,
159.4 (s, CN4)
Ϫ11.1
7
8
9
1.14 (t, 18 H, J = 4)
1.36 (t, 18H, J = 4)
1.37 (t, 18H, J = 4)
5.46 (s, 4H, CH2)
7.27 (m, 10H, Ph)
1.52 (t, 6H, J = 7.2, CH3)
4.36 (q, 4H, J = 7.3, CH2)
7.27–7.59 (m, 6H, Ph)
7.85–7.89 (m, 4H, Ph)
13.2 (t, J = 16, CH3), 50.8, 128.3,
128.5, 128.6, 134.3, 159.5 (br, CN4)
13.4 (t, J = 16, CH3)
14.4, 42.4, 158.9 (s, CN4)
13.5 (t, J = 16, CH3),
123.5, 129.0, 129.3, 135.4,
159.4 (s, CN4) 160.9(s, CN4)
13.6 (t, J = 16, CH3), 17.8, 128.6,
130.2, 133.1, 135.9, 160.8 (s, CN4)
Ϫ11.5
Ϫ11.2
Ϫ11.0
10
11
12
1.41 (t, 18H, J = 4)
1.74 (t, 12H, J = 4)
2.04 (s, 12H, CH3)
Ϫ11.5
Ϫ1.37
16.4
7.20–7.23 (m, 4H, Ph)
7.31–7.38 (m, 2H, Ph)
7.20–7.26 (m, 6H, Ph)
7.40–7.54 (m, 14H, Ph)
12.7 (t, J = 16, CH3), 123.3,
127.8 (t, J = 4), 128.7, 128.9, 129.8,
130.8 (t, J = 6), 160.9 (s, CN4)
8.1, 13.9 (t, J = 14, CH2), 17.7,
128.6, 130.3, 133.2, 135.9,
160.4 (s, CN4)
12.6 (t, J = 19, CH3), 123.7, 129.1,
129.3, 135.2, 157.7 (s, CN4)
12.5 (t, J = 19, JPt–P = 30),
14.4 (s, CH3), 42.4 (s, CH2),
157.2 (s, CN4)
1.10 (q, 18H, J = 7)
1.79 (m, 12H)
2.05 (s, 12H, CH3)
7.21–7.26 (m, 4H, Ph)
7.33–7.38 (m, 2H, Ph)
7.47–7.59 (m, 6H, Ph)
7.80–7.84 (m, 4H, Ph)
1.52 (t, 6H, J = 7, CH3)
4.35 (q, 4H, J = 7, –CH2)
13
14
1.44 (t, 18H, J = 4)
Ϫ14.8
(JPt–P = 2402)
Ϫ14.9
1.43 (t, 18H, J = 4
JPt–P = 28)
JPt–P = 2386
15
16
1.22 (m, 18H)
2.04 (m, 12H)
7.28–7.41 (m, 6H, Ph)
7.56–7.63 (m, 4H, Ph)
8.5 (s, JPt–C = 22, CH3),
10.5
(JPt–P = 3054)
16.5 (br q, CH3), 123.9, 128.5,
128.9, 135.4, 159.2 (s, CN4)
8.9 (br d, J = 1, CH3),
1.21 (t, 6H, J = 8)
1.27 (t, 6H, J = 8)
1.92–2.22 (m, 12H)
7.36–7.45 (m, 6H, Ph)
7.72–7.75 (m, 4H, Ph)
72.8
19.4, (d, J = 28, CH2),
23.7 (dd, J = 14, 29, CH2), 124.2,
128.5, 128.8, 135.6, 159.8 (s, CN4)
8.8 (dd, J = 1, JPt–C = 25, CH3)
18.7 (d, J = 36, JPt–C = 31, CH3)
23.6 (d, J = 9, 36, CH2), 124.7,
128.7, 128.9, 135.4, 158.0 (s, CN4)
9.0 (br d, J = 1, JPt–C = 27, CH3)
17.9 (s, CH3)
17
18
1.11 (t, 6H, J = 8)
1.17 (t, 6H, J = 8)
1.80–2.15 (m, 12H)
7.35–7.46 (m, 6H, Ph)
7.66–7.69 (m, 4H, Ph)
54.1
(JPt–P = 3036)
1.19 (t, 6H, J = 8)
1.25 (t, 6H, J = 8)
1.82–2.39 (m, 12H)
1.88 (s, 12H, CH3)
7.08–7.11 (m, 4H, Ph)
7.22–7.27 (m, 2H, Ph)
53.7
(JP–P = 3076)
19.0 (d, J = 36, JPt–C = 34, CH3)
23.6 (dd, J = 9, 36, CH2), 128.2,
129.9, 133.3, 136.2, 160.3 (s, CN4)
a Obtained in CDCl3 at 25 ЊC. Peak positions were referenced to internal SiMe4. b Obtained in CDCl3 at 25 ЊC. Peak positions were referenced to
internal SiMe4. c Obtained in CDCl3 at 25 ЊC. Peak positions were referenced to external 85% H3PO4. Abbreviation: t, triplet; q, quartet; dd, doublet
of doublets; dt, doublet of triplets; m, multiplet.
Fig. 3 ORTEP drawing of 6 showing the atom-labeling scheme and
50% probability thermal ellipsoids. Selected bond lengths (Å) and
angles (Њ): Pd1–P1 2.3237(7), Pd1–S1 2.3415(7), S1–C4 1.717(3), N1–C4
1.343(3), N1–N2 1.352(4), N2–N3 1.276(4), N3–N4 1.359(4), N4–C4
1.326(4); P1–Pd1–S1 87.32(3), C4–S1–Pd1 100.14(9).
Fig. 4 ORTEP drawing of 9 showing the atom-labeling scheme and
50% probability thermal ellipsoids. Selected bond lengths (Å) and
angles (Њ): Pd1–S1 2.3248(8), Pd1–P1 2.3341(8), S1–C4 1.719(3), N1–C4
1.328(4), N1–N2 1.362(4), N2–N3 1.288(4), N3–N4 1.361(3), N4–C4
1.357(4), N4–C5 1.439(4); S1–Pd1–P1 93.91(3), C4–S1–Pd1 105.25(10).
Treatment of 9 and 10 with two equivalents of benzoyl
chloride (PhCOCl) at room temperature give organic sulfides,
C6H5(CO)–S–CN4–C6H5) (19, 88%) and C6H5(CO)–S–CN4-2,6-
Me2C6H3 (20, 85%), respectively (eqn. (5)). In addition, com-
plex 9 reacts with two equivalents of 2-thiophenecarbonyl
chloride (C4H3SCOCl) to give C4H3S(CO)–S–CN4–C6H5 (21,
79%). However, the reaction of 9 with iodobenzene does not
occur and results only in the recovery of the starting material.
These organic sulfides are isolated as white crystals without
requiring column chromatography and have been characterized
by IR, NMR, and elemental analyses. Compound 20 has been
D a l t o n T r a n s . , 2 0 0 3 , 3 3 5 7 – 3 3 6 4
3360

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Table 3 X-Ray data collection and structure refinement for 4–6, 9, 14 and 18
4
5ؒH2O
6
9
14
18ؒ2H2O
Formula
Mw
T/K
C8H18N2P2S2Ni
327.01
293(2)
C14H32N2OP2S2Pt C14H28N8P2PdS2 C20H28N8P2S2Pd C12H28N8P2S2Pt
C28H46N8O2P2PtS2
847.88
2939(2)
565.57
293(2)
540.90
293(2)
612.96
293(2)
605.57
293(2)
Crystal size/mm
Crystal system
Space group
0.28 × 0.22 × 0.16 0.08 × 0.08 × 0.08 0.62 × 0.60 × 0.42 0.32 × 0.30 × 0.28 0.16 × 0.14 × 0.12 0.24 × 0.20 × 0.16
Monoclinic
P21/n
Tetragonal
P42/nmc
Monoclinic
P21/c
Monoclinic
P21/n
Monoclinic
P21/c
Orthorhombic
C2221
a/Å
b/Å
c/Å
6.183(1)
7.292(1)
16.744(3)
91.91(2)
754.5(2)
2
1.439
1.749
340
12.207(2)
12.207(2)
16.112(6)
12.015(2)
8.3887(4)
11.8788(9)
96.75(1)
1188.9(2)
2
1.511
1.107
552
6.191(1)
17.205(3)
12.664(2)
100.53(2)
1326.1(4)
2
1.535
1.003
624
11.367(2)
8.531(1)
11.587(2)
93.63(1)
1121.3(3)
2
1.794
6.599
592
12.155(3)
19.510(5)
15.766(3)
β/Њ
V/Å3
2401(1)
4
1.565
6.154
1112
3739(1)
4
1.506
3.986
1704
Z
Dc/g cmϪ3
µ/mmϪ1
F(000)
Tmin
Tmax
0.2464
0.2892
1458
0.2659
0.2832
1156
0.0319
0.0536
2186
0.4630
0.4770
2545
0.5727
0.8699
2066
0.4370
0.8131
1825
No. of reflns. measured
No. of reflns. unique
1329
1155
2075
2320
1963
1825
No. of reflns. with I > 2σ(I ) 1235
708
66
1997
125
0.487
Ϫ0.557
1.042
0.0263
0.0723
0.0271
0.0731
2032
151
0.282
Ϫ0.343
1.041
0.0264
0.0638
0.0325
0.0675
1588
115
0.440
Ϫ0.464
1.073
0.0242
0.0550
0.0361
0.0600
1682
189
No. of params. refined
Max. in ∆ρ/e ÅϪ3
Min., in ∆ρ/e ÅϪ3
GOF on F 2
71
0.220
Ϫ0.182
1.086
0.0237
0.0629
0.0262
0.0646
0.862
Ϫ0.529
1.017
0.0397
0.0814
0.0805
0.0962
1.604
Ϫ0.570
1.097
0.0378
0.0963
0.0424
0.0995
R
wR2
a
R (all data)
wR2 a (all data)
2
a wR2 = Σ[w(Fo2 Ϫ Fc2)2]/Σ[w(Fo ) 2]1/2
.
Fig. 5 ORTEP drawing of 14 showing the atom-labeling scheme and
50% probability thermal ellipsoids. Selected bond lengths (Å) and
angles (Њ): N4–C17 1.425(11), Pt1–P1 2.313(1), Pt1–S1 2.337(1), S1–C4
1.715(5), N1–C4 1.330(6), N1–N2 1.347(7), N2–N3 1.288(8), N3–N4
1.356(7), N4–C4 1.342(6), N4–C5 1.465(7); P1–Pt1–S1 87.65(5), C4–
S1–Pt1 102.2(2).
Fig. 6 ORTEP drawing of 18 showing the atom-labeling scheme and
50% probability thermal ellipsoids. Selected bond lengths (Å) and
angles (Њ): Pt1–P1 2.227(3), Pt1–S1 2.365(3), S1–C1 1.741(12), N1–C1
1.312(13), N1–N2 1.352(13), N1–C2 1.450(15), N2–N3 1.257(15), N3–
N4 1.374(14), N4–C1 1.292(17), P1–Pt1–S1 90.93(12), C1–S1–Pt1
102.3(4).
group, which might explain the formation of thioacyl com-
pounds 19–21. On the other hand, the formation of a dimeric
compound 22 with an S–S bond, which is apparently a reduc-
tive-elimination product of the two thiolato groups, strongly
suggests that the reaction proceeds via a three-coordinate
intermediate ([Pd(PR3)(SCN4R)2]) formed by phosphine dis-
sociation. Otherwise, complex 10 possessing trans thiolate
ligands cannot fulfill the requirement of the cis orientation of
the groups to be eliminated unless the reaction proceeds in an
intermolecular fashion.
(5)
structurally characterized by X-ray diffraction, and its ORTEP
drawing in Fig. 7 gives definitive evidence for the proposed
structure. Interestingly, treatment of 10 with benzoyl chlor-
ide affords a dithio compound, [SCN4-2,6-Me2C6H3]2 (22),
although in a trace amount (Fig. 8). The present results do
not give detailed information about the mechanism, but the
electrophilic acyl halide appears to have abstracted the thiolate
The coordinated isothiocyanato (NCS) lignad is known
to react with various electrophiles to give isothiocyanide
compounds,28 but other chemical properties such as dipolar
cycloaddition of pseudo-halides such as azide (N3) or cyanate
(CN) are relatively unexplored. In this regard, we have investi-
gated the cycloaddition reactivity of isothiocyanato complexes
toward isocyanides to check whether heterocyclic compounds
D a l t o n T r a n s . , 2 0 0 3 , 3 3 5 7 – 3 3 6 4
3361

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In this work we have shown that di(azido)bis(phosphine)
complexes of Group 10 metals {M(N3)2(PR3)2} react with
organic isothiocyanates to give tetrazole-containing thiolato
complexes or isothiocyanato complexes, depending upon the
nature of the organic isothiocyanates. Treatment of tetrazole-
thiolate complexes with benzoyl halide derivatives afford
various organic sulfides.
Experimental
All manipulations of air-sensitive compounds were performed
under N2 or Ar with the use of standard Schlenk techniques.
Solvents were distilled from Na–benzophenone. The analytical
laboratories at Basic Science Institute of Korea and at
Kangnung National University carried out the elemental analy-
ses. IR spectra were recorded on a Perkin Elmer BX spectro-
photometer. NMR (1H, 13C{1H} and 31P{1H}) spectra were
obtained on JEOL Lamda 300 MHz spectrometer. Chemical
shifts were referenced to internal Me4Si and to external 85%
H3PO4. Pd(N3)2L2 (L = PMe3, PEt3, PMe2Ph and L–L = depe)
and Pt(N3)2L2 (L = PMe3, PEt3 and L–L = depe) were prepared
by ligand-exchange reactions of Pd(N3)2(tmeda)29 (tmeda =
N,N,NЈ,NЈ-tetramethylethylenediamine) and Pt(N3)2(COD)29
(COD = 1,5-cyclooctadiene) with the appropriate ligands.
Ni(N3)2L2 (L = PMe3) was prepared by the literature method.30
Fig. 7 ORTEP drawing of 20 showing the atom-labeling scheme and
50% probability thermal ellipsoids. Selected bond lengths (Å) and
angles (Њ): S1–C9 1.779(7), S1–C10 1.807(9), O1–C10 1.090(11), N1–N2
1.329(7), N1–C9 1.345(8), N1–C1 1.467(7), N2–N3 1.297(8), N3–N4
1.301(9), N4–C9 1.293(9); C9–S1–C1 96.9(5).
Preparation of M(NCS)2L2 (M ؍ Pd, L ؍ PMe3 (1), PEt3 (2),
PMe2Ph (3); M ؍ Ni, L ؍ PMe3 (4); M ؍ Pt, L ؍ PEt3 (5))
To a Schlenk flask containing Pd(N3)2(PMe3)2 (0.312 g, 0.91
mmol) was added CH2Cl2 (10 cm3) and trimethylsilyl iso-
thiocyanate (0.257 cm3, 1.82 mmol) in that order. After stirring
the reaction mixture at room temperature for 24 h, the solvent
was removed completely and the resulting solids were washed
with hexane and dried under vacuum to give pale yellow
solids. Recrystallization from CH2Cl2–hexane gave pale yellow
crystals of cis-Pd(NCS)2(PMe3)2 (1, 0.371 g, 90%). Data for
cis-Pd(NCS)2(PMe3)2 (1): νmax/cmϪ1 (NCS): 2089 (vs) (Found:
C, 25.42; H, 4.79; N, 6.95. C8H18N2S2P2Pd requires C, 25.64; H,
4.84; N, 7.48%); δH (300 MHz in DMSO-d6): 1.62–1.66 (br d,
18H, PMe3); δC (75 MHz in DMSO-d6) 15.0 (s, P(CH3)3),
15.2 (br s), 15.5 (s, P(CH3)3), 132.6 (s, NCS); δP (120 MHz in
DMSO-d6) 3.3 (s).
Fig. 8 ORTEP drawing of 22 showing the atom-labeling scheme and
50% probability thermal ellipsoids. Selected bond lengths (Å) and
angles (Њ): S1–S2 2.026(2), S1–C9 1.764(6), S2–C18 1.757(6), N1–C9
1.343(7), N1–N2 1.377(6), N2–N3 1.295(7), N3–N4 1.379(7), N4–C9
1.313(7), N5–C18 1.342(7), N5–N6 1.365(7), N6–N7 1.295(7), N7–N8
1.365(7), N8–C18 1.303(7); C9–S1–S2 100.6(2), C18–S2–S1 100.4(2).
Complexes 2–5 were prepared similarly. Data for trans/cis-
Pd(NCS)2(PEt3)2 (2, 90%): νmax/cmϪ1 (NCS): 2098 (vs) (Found:
C, 36.94 H, 6.74; N, 6.05. C14H30N2S2P2Pd requires C, 36.64; H,
6.59; N, 6.10%); δH (300 MHz in CDCl3): 1.22 (br q, 18H,
P(CH2CH3)3), 1.81–2.09 (m, 12H, P(CH2CH3)3); δC (75 MHz
in CDCl3): 7.94 (s, P(CH2CH3)3), 8.13 (s, P(CH2CH3)3), 14.6 (t,
J = 14 Hz, P(CH2CH3)3), 15.1 (t, J = 14 Hz, P(CH2CH3)3),
131.7 (s, NCS), 135.2 (NCS); δP (120 MHz in CDCl3) 22.6 (s),
24.5 (s). Data for trans/cis-Pd(NCS)2(PMe2Ph)2 (3, 97%):
νmax/cmϪ1 (NCS): 2099, 2077 (vs) (Found: C, 43.48; H, 4.46; N,
6.00. C18H22N2S2P2Pd requires C, 43.34; H, 4.44; N, 5.62%);
δH (CDCl3 in 300 MHz): 1.93 (s, 12H, Me), 7.27–7.64 (10H,
Ph); δC (75 MHz in CDCl3) 12.2 (t, J = 16 Hz, PMe2Ph), 129.0,
130.8, 131.0, 131.5 (s, Ph); δP (120 MHz in CDCl3) 0.67, Ϫ6.29.
Data for trans-Ni(NCS)2(PMe3)2 (4, 89%): νmax/cmϪ1 (NCS):
2105 (vs) (Found: C, 29.69; H, 5.68; N, 8.56. C8H18N2S2P2Ni
requires C, 29.38; H, 5.55; N, 8.57%); δH (300 MHz in CDCl3)
1.33 (br s, 18H, PMe3); δC (75 MHz in CDCl3) 12.3 (s, PMe3),
145.0 (s, NCS); δP (120 MHz in CDCl3) Ϫ13.7(s). Data for
cis-Pt(NCS)2(PEt3)2 (5, 76 %): νmax/cmϪ1 (NCS): 2096 (vs)
(Found: C, 29.66; H, 5.37; N, 4.65. C14H30N2S2P2Pd requires C,
30.71; H, 5.52; N, 5.12%); δH (DMSO-d6 in 300 MHz) 1.10 (br
q, 18H, P(CH2CH3)3), 1.92 (m, 12H, P(CH2CH3)3); δC (75 MHz
in DMSO-d6) 7.99 (s, P(CH2CH3)3), 15.4 (br d, P(CH2CH3)3),
134.1 (NCS); δP (120 MHz in DMSO-d6) Ϫ5.13 (s, JPt–P = 3333
Hz). Complex 4 was independently prepared by the reaction of
(6)
are formed. The reaction of trans-Ni(NCS)2(PMe3)2 (4) with
two equivalents of tert-butyl isocyanide smoothly proceeds to
give an isocyanide adduct, [Ni(PMe3)2(NCS)2]ؒ2(t-Bu)NC (23),
in 76% yield as shown in eqn. (6).
The IR spectrum of 23 displays two strong bands at 2051 and
2196 cmϪ1 assigned to ν(N᎐C᎐S) and ν(N᎐C). A virtual triplet
᎐
᎐ ᎐
᎐
due to the two PMe3 ligands both in the H and 13C NMR
indicates the trans form of the complex. One singlet in the
31P NMR spectrum also supports the trans symmetry. The
integration ratio of the alkyl protons on the 1H NMR spectrum
of 23 is also consistent with that for the proposed structure.
One signal corresponding to the NCS carbon is observed at 123
ppm in the 13C NMR spectrum. Even after several recrystalliz-
ations, the tert-butyl isocyanide has not been eliminated from
the complex (adduct), suggesting its strong association (or
interaction) with the coordination sphere of the metal. At
present, we do not have any information about the exact mode
of interaction between the tert-butyl isocyanide and a metal
center or between the isothiocynato group because of the lack
of crystallographic information. However, the spectral data
clearly indicate that complex 23 is not a cycloaddition product.
1
31,32
Ni(SCN)2 with 2 equiv. or excess PMe3.
D a l t o n T r a n s . , 2 0 0 3 , 3 3 5 7 – 3 3 6 4
3362

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Preparation of Pd{S[CN4(R)]}2L2 (L ؍ PMe3, R ؍ allyl (6),
benzyl (7), ethyl (8), phenyl (9), 2,6-dimethylphenyl (10);
L ؍ PMe2Ph, R ؍ phenyl (11); L ؍ PEt3, R ؍ 2,6-dimethylphenyl
(12)
phenyl C–H); δC (75 MHz in CDCl3) 125.0, 128.6, 129.6, 130.8,
133.7, 133.9, 136.1, 138.5, 145.7, 175.1 (s, C᎐O).
᎐
Reaction of 4 with tert-butyl isocyanide
To a Schlenk flask containing Pd(N3)2(PMe3)2 (0.346 g, 1.01
mmol) was added CH2Cl2 (7 cm3) and allyl isothiocyanate
(0.196 cm3, 2.02 mmol). After stirring the reaction mixture at
room temperature for 18 h, the solvent was removed and the
resulting solids were washed with hexane and dried to give
yellow solids. Recrystallization from CH2Cl2–diethyl ether gave
To a Schlenk flask containing Ni(NCS)2(PMe3)2 (0.294 g,
0.90 mmol) was added CH2Cl2 (3 cm3) and tert-butyl isocyanide
(0.203 cm3, 1.8 mmol). After stirring the reaction mixture at
room temperature for 18 h, the solvent was removed and the
resulting solids were washed with diethyl ether and dried to give
orange solids. Recrystallization from CH2Cl2–diethyl ether gave
orange crystals of [Ni(PMe3)2(NCS)2]ؒ2(t-BuNC), (23, 0.336 g,
yellow crystals of trans-Pd{S[CN (CH CH᎐CH )]} (PMe ) (6,
᎐
4
2
2
2
3 2
76%); νmax/cmϪ1 (N᎐C): 2196 (vs), ν(NCS) 2051 (vs) (Found:
᎐
0.410 g). Analytical and NMR data of the tetrazole-thiolato
complexes are summarized in Tables 1 and 2.
᎐
C, 43.57; H, 7.48; N, 11.36. C18H36N4S2P2Ni requires C, 43.83;
Complexes 7–12 were analogously prepared.
H, 7.36; N, 11.36%); δH (300 MHz in CDCl3) 1.61 (s, 18H,
C(CH3)3), 1.69 (t, 18H, J = 4 Hz, PMe3); δC (75 MHz in CDCl3):
15.4 (t, J = 17 Hz, PMe3), 30.4 (s, C(CH3)3), 59.3 (s, C(CH3)3),
122.7 (s, NCS); δP (120 MHz in CDCl3) 6.34(s).
Preparation of Pt{S[CN4(R)]}2L2 (L ؍ PMe3, R ؍ Ph (13), Et
(14); L ؍ PEt3, R ؍ Et (15))
To a Schlenk flask containing Pt(N3)2(PMe3)2 (0.266 g, 0.62
mmol) was added CH2Cl2 (5 cm3) and phenyl isothiocyanate
(0.148 cm3, 1.24 mmol). The initial pale yellow solution slowly
turned to an orange solution. After stirring the reaction
mixture at 60 ЊC for 5 h, the solvent was removed and the
resulting solids were washed with diethyl ether and dried to give
white solids. Recrystallization from CH2Cl2–diethyl ether gave
white crystals of trans-Pt{S[CN4(Ph)]}2(PMe3)2 (13, 0.304 g).
Complexes 14 and 15 were prepared analogously.
X-Ray structure determination
All X-ray data were collected with a Siemens P4 diffractometer
equipped with a Mo X-ray tube. Intensity data intensity data
were empirically corrected for absorption with ψ-scan data.
All calculations were carried out with the use of SHELXTL33
programs. All structures was solved by direct methods. All non-
hydrogen atoms were refined anisotropically. All hydrogen
atoms were generated in ideal positions and refined in a riding
mode. Details on crystal data, intensity collection, and refine-
ment details for 4–6, 9, 14 and 18 are given in Table 3.
Preparation of M{S[CN4(R)]}2L2 (R ؍ Ph, M ؍ Pd (16), Pt
(17); R ؍ 2,6-Me2C6H3, M ؍ Pt (18), L–L ؍ depe)
Crystal data for C6H5(CO)–S–CN4-2,6-Me2C6H3) (20) are as
follows: C16H14N4OS, M = 310.37, triclinic, space group P1,
¯
To a Schlenk flask containing Pd(N3)2(depe) (0.250 g, 0.63
mmol) was added CH2Cl2–THF (4 : 6 cm3) and phenyl
isothiocyanate (0.151 cm3, 1.26 mmol). The initial pale yellow
solution slowly turned to an orange solution. After stirring the
reaction mixture at 60 ЊC for 5 h, the solvent was removed and
the resulting solids were washed with diethyl ether and dried to
give white solids. Recrystallization from CH2Cl2–hexane gave
white crystals of Pd{S[CN4(R)]}2(depe) (16, 0.320 g).
a = 7.956(3), b = 9.962(3), c = 11.165(3) Å, α = 91.151(18),
β = 107.51(2)Њ, γ = 111.21(2)Њ, V = 778.5(4) Å3, Z = 2, T = 295(2)
K, µ = 0.215 mmϪ1, 2905 reflections measured, 2697 unique
(Rint = 0.284), from which 1440 with I > 2σ(I ) were used in
refinements. Final R1 and wR2 values were 0.0995 and 0.2505,
respectively.
Crystal data for (SCN4-2,6-Me2C6H3)2 (22) are as follows:
C18H18N8S2, M = 410.52, monoclinic, space group P21/c, a =
11.153(3), b = 13.732(3), c = 13.616(4) Å, β = 93.46(2)Њ, V =
2074.4(10) Å3, Z = 4, T = 295(2) K, µ = 0.277 mmϪ1, 3692
reflections measured, 3494 unique (Rint = 0.0494), from which
1504 with I > 2σ(I ) were used in refinements. Final R1 and wR2
values were 0.0750 and 0.1506, respectively.
Complexes 17 and 18 were prepared analogously.
Reactions of 9 and 10 with benzoyl chloride (PhCOCl) and
2-thiophenecarbonyl chloride (C4H3SCOCl)
To a CH2Cl2 (15 ml) solution containing trans-Pd{S[CN4-
(Ph)]}2(PMe3)2, (9, 0.520 g, 0.78 mmol) was added benzoyl
chloride (0.180 cm3, 1.55 mmol) at room temperature. After
stirring the reaction mixture for 24 h, the solvent was removed,
and the resulting residue was extracted with excess diethyl ether.
The collected extracts were again evaporated to give crude
solids, which were recrystallized from diethyl ether–hexane to
give white crystals of C6H5(CO)–S–CN4(C6H5) (19, 0.549 g,
88%). The remaining residues were identified as PdCl2(PMe3)2
in quantitative yields, confirmed by IR and NMR spectroscopy.
Data for C6H5(CO)–S–CN4(C6H5): νmax/cmϪ1: 1686 (s) (Found:
C, 59.45; H, 3.60; N, 19.95. C14H10N4OS requires C, 59.96; H,
3.57; N, 19.85%); δH (300 MHz in CDCl3) 7.46–7.69 (m, 8H,
Ph), 7.85–7.90 (m, 2H, Ph); δC (75 MHz in CDCl3) 125.0, 128.1,
CCDC reference numbers 210413–210420.
See http://www.rsc.org/suppdata/dt/b3/b305341p/ for crystal-
lographic data in CIF or other electronic format.
Acknowledgements
This work was supported by Grant R05-2002-000-00559-0
from the Basic Research Program of the Korea Science &
Engineering Foundation.
References
1 For reviews: W. Beck, J. Organomet. Chem., 1990, 383, 143;
J. Strahle, Comments Inorg. Chem., 1985, 4, 295; S. Cenini and
G. La Monica, Inorg. Chim. Acta, 1976, 18, 279; Z. Dori and
R. F. Ziolo, Chem. Rev., 1973, 73, 247.
2 W. Beck and W. P. Fehlhammer, Angew. Chem., Int. Ed., 1967, 6,
169; W. Beck, M. Bander, W. P. Fehlhammer, P. Pohlmann and
H. Schachl, J. Inorg. Nucl. Chem. Lett., 1968, 4, 143; W. Beck,
W. P. Fehlhammer, W. P. Pollmann and H. Schachl, Chem. Ber.,
1969, 102, 1976; W. Beck, W. P. Fehlhammer, H. Bock and
M. Bauder, Chem. Ber., 1969, 102, 3637; W. Beck and K. Schorpp,
Chem. Ber., 1975, 108, 3317; J. Erbe and W. Beck, Chem. Ber., 1983,
116, 3867; P. Kreutzer, C. Weis, H. Bock, J. Erbe and W. Beck, Chem.
Ber., 1983, 116, 2691; J. Geisenberger, J. Erbe, J. Heidrich, U. Nagel
and W. Beck, Z. Naturforsch., Teil B, 1987, 42, 55.
129.3, 129.6, 130.7, 133.7, 134.4, 135.2, 146.2, 183.7 (s, C᎐O).
᎐
Data for C6H5(CO)–S–CN4-2,6-Me2C6H3) (20, 85%): νmax/cmϪ1
:
1699 (s, CO) (Found: C, 61.99; H, 4.63; N, 18.12. C16H14N4OS
requires C, 61.92; H, 4.55; N, 18.05%); δH (300 MHz in CDCl3)
2.03 (s, 6H, Me), 7.18–7.20 (m, 2H, Ph), 7.32–7.37 (m, 1H, Ph),
7.45–7.51 (m, 2H), 7.62–7.68 (m, 1H, Ph), 7.85–7.87 (m, 2H,
Ph); δC (75 MHz in CDCl3) 17.5 (s, Me), 128.1, 128.8, 129.1,
129.2, 131.0, 134.5, 135.1, 135.9, 147.6, 183.3 (C᎐O). Data for
᎐
C4H3S(CO)–S–CN4–C6H5 (21, 79%): νmax/cmϪ1: 1677, 1659 (s,
CO) (Found: C, 49.72; H, 2.85; N, 19.39. C12H8N4OS requires
C, 49.98; H, 2.80; N, 19.43%); δH (300 MHz in CDCl3) 7.19 (dd,
1H, J = 4 Hz, thiophenyl C–H), 7.56 (br s, 5H, Ph), 7.79 (dd,
1H, J = 1 Hz, thiophenyl C–H), 7.86 (dd, 1H, J = 4 Hz, thio-
3 P. Kreutzer, C. Weis, H. Boehme, T. Kemmerich, W. Beck,
C. Spencer and R. Mason, Z. Naturforsch., Teil B, 1972, 27, 745.
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View Article Online
4 M. Wehlan, R. Thiel, J. Fuchs, W. Beck and W. P. Fehlhammer,
J. Organomet. Chem., 2000, 613, 159.
5 S. S. Wasburne and W. R. Jr. Peterson, J. Organomet. Chem., 1971,
33, 337.
6 S. Kozima, I. Itano, N. Mihara, K. Sisido and T. Isida, J. Organomet.
Chem., 1972, 44, 117.
7 R. F. Ziolo, A. P. Gaughan, Z. Dori, C. G. Pierpont and
R. Eisenberg, Inorg. Chem., 1971, 10, 1289; R. F. Ziolo, J. A. Thich
and Z. Dori, Inorg. Chem., 1972, 3, 626; A. P. Gaughan,
K. S. Bowman and Z. Dori, Inorg. Chem., 1972, 3, 601; Z. Dori and
R. F. Ziolo, Chem. Rev., 1973, 73, 248.
16 F. Sato, M. Etoh and M. Sato, J. Organomet. Chem., 1974, 70, 101.
17 R. J. Deeth, K. C. Molloy, M. F. Mahon and S. Whittaker,
J. Organomet. Chem., 1992, 430, 25.
18 W. Beck, K. Burger and M. Keubler, Z. Anorg. Allg. Chem., 1977,
428, 173.
19 H. Nöth, W. Beck and K. Burger, Eur. J. Inorg. Chem., 1998, 93.
20 G. Wilkinson, R. D. Gillard and J. A. McCleverty, Comprehensive
Coordination Chemistry, Pergamon Press, New York 1987, vol. 2,
p. 225.
21 R. Clark and G. J. Palenik, Inorg. Chem., 1970, 9, 2754; G. J. Palenik,
M. Mathew, W. L. Steffen and G. Beran, J. Am. Chem. Soc., 1975,
97, 1059.
22 Y. S. Wong, S. Jacobson, P. C. Chieh and A. J. Carty, Inorg. Chem.,
1974, 13, 284.
8 L. Busetto, A. Palazzi and R. Ros, Inorg. Chim. Acta, 1975, 13, 233.
9 W. Rigby, P. M. Bailby, J. A. McCleverty and P. M. Maitlis, J. Chem.
Soc., Dalton Trans., 1978, 371.
10 W. R. Ellis and W. L. Purcell, Inorg. Chem., 1982, 21, 834; J. H. Hall,
R. L. De la Vega and W. L. Purcell, Inorg. Chim. Acta, 1985, 102,
157.
11 T. Kemmerich, J. H. Nelson, N. E. Takach, H. Boeheme,
B. Jablonski and W. Beck, Inorg. Chem., 1982, 21, 1226.
12 P. Paul and K. Nag, Inorg. Chem., 1987, 26, 2969; P. Paul,
S. Chakladar and K. Nag, Inorg. Chim. Acta, 1990, 170, 27; R. Das,
P. Paul, K. Nag and K. Venkatsubrmanian, Inorg. Chim. Acta, 1991,
182, 221.
23 J. J. MacDougall, A. W. Verstuyft, L. W. Cary and J. H. Nelson,
Inorg. Chem., 1980, 19, 1036.
24 J. MacDougall, J. H. Nelson, M. W. Babich, C. C. Fuller and
R. A. Jacobson, Inorg. Chim. Acta, 1978, 27, 201.
25 R. Hübener, K. Ortner, J. Strähle and U. Abram, Inorg. Chim. Acta,
1996, 244, 109.
26 T. T. Bamgboye and D. B. Sowerby, Polyhedron, 1986, 5, 1487.
27 U. Behrens, K. Hoffmann, J. Kopf and J. Moritz, J. Organomet.
Chem., 1976, 117, 28.
13 R. Guilard, S. S. Gerges, A. Tabard, P. Richard, M. A. El Borai
and C. Lecomte, J. Am. Chem. Soc., 1987, 109, 7228; N. Jagerovic,
J.-M. Barbe, M. Farnier and R. Guilard, J. Chem. Soc., Dalton
Trans., 1988, 2569.
14 Y.-J. Kim, Y.-S. Kwak, Y.-S. Joo and S. W. Lee, J. Chem. Soc., Dalton
Trans., 2002, 144; Y.-J. Kim, Y.-S. Joo, J.-T. Han, W. S. Han and
S. W. Lee, J. Chem. Soc., Dalton Trans., 2002, 3611; Y.-J. Kim,
Y.-S. Kwak and S. W. Lee, J. Organomet. Chem., 2000, 603, 152;
Y.-J. Kim, D.-H. Kim, J.-Y. Lee and S. W. Lee, J. Organomet. Chem.,
1997, 538, 189.
28 J. H. Lee, B.-S. Yoo and S. W. Lee, Inorg. Chim. Acta, 2001, 321,
75.
29 Y.-J. Kim, J.-C. Choi and K.-H. Park, Bull. Korean Chem. Soc.,
1994, 15, 690.
30 K. Bowman and Z. Dori, Inorg. Chem., 1970, 9, 395.
31 K. A. Jensen and O. Dahl, Acta Chem. Scand., 1968, 22, 1044.
32 A. Merle, M. F. Obier, M. Dartiguenave and Y. Dartiguenave, Acad.
Sci., Ser. C., 1971, 272, 1956.
33 G. M. Sheldrick, SHELX-97, University of Göttingen, Germany,
1997.
15 P. Kreutzer, Ch. Weis, H. Bock, J. Erbe and W. Beck, Chem. Ber.,
1983, 116, 2691.
34 L. J. Farrugia, ORTEP-3 for Windows, University of Glasgow,
1997.
D a l t o n T r a n s . , 2 0 0 3 , 3 3 5 7 – 3 3 6 4
3364