Formation of Homo- and Heteronuclear Platinum(II) and Palladium(II) Carbene Complexes in the Reactions of Coordinated Isocyanides with Aminothiazaheterocycles

Article abstract of DOI:10.1134/S1070363218100158

The reaction of 5-(trifluoromethyl)-1,3,4-thiadiazol-2-amine with cis-dichlorobis(2,6-dimethylphenyl isocyanide)platinum(II) (cis-[PtCl₂(CNXyl)₂], Xyl = 2,6-Me₂C₆H₃) gave platinum(II) monocarbene comp

Full text of DOI:10.1134/S1070363218100158

ISSN 1070-3632, Russian Journal of General Chemistry, 2018, Vol. 88, No. 10, pp. 2119–2124. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © A.S. Mikherdov, Yu.A. Orekhova, and V.P. Boyarskii, 2018, published in Zhurnal Obshchei Khimii, 2018, Vol. 88, No. 10, pp. 1677–
1
683.
Formation of Homo- and Heteronuclear Platinum(II)
and Palladium(II) Carbene Complexes in the Reactions
of Coordinated Isocyanides with Aminothiazaheterocycles
a
a
a
A. S. Mikherdov , Yu. A. Orekhova , and V. P. Boyarskii *
a
St. Petersburg State University, Universitetskaya nab. 7–9, St. Petersburg, 199034 Russia
*
e-mail: v.boiarskii@spbu.ru
Received July 26, 2018
Abstract—The reaction of 5-(trifluoromethyl)-1,3,4-thiadiazol-2-amine with cis-dichlorobis(2,6-dimethyl-
phenyl isocyanide)platinum(II) (cis-[PtCl (CNXyl) ], Xyl = 2,6-Me ) gave platinum(II) monocarbene
2
2
2 6 3
C H
complex whose deprotonation with an organic base generated a nucleophilic species capable of reacting with
palladium(II) and platinum(II) bis(isocyanide) complexes to afford homo- and heteronuclear isocyanide/
carbene structures.
Keywords: platinum(II) diaminocarbene complexes, palladium(II) diaminocarbene complexes, heteronuclear
carbene complexes, isocyanide ligands, aminothiazaheterocycles
DOI: 10.1134/S1070363218100158
At present, reactions of nitrogen nucleophiles with
diversity [21–24]. In this case, the carbene fragment
contains an additional sulfur atom, so that the resulting
carbene complexes can be regarded as convenient
models for studying certain weak interactions in
transition metal complexes, primarily chalcogen bonds
which were not studied previously in these systems but
now attract keen interest 25–28]. Furthermore, weak
interactions in aminocarbene complexes containing a
thiazole fragment play an important role both in the
solid state and in solution [22] and affect not only
isomerization equilibria involving different carbene
complexes but also their reactivity and regioselectivity
of reactions [21].
isocyanide ligands in late transition metal complexes,
especially gold, platinum, and palladium complexes,
are extensively studied [1–3]. The reason is that the
diaminocarbene complexes formed in reactions with
mono-N-nucleophiles exhibit unique catalytic [4–13]
and biological properties [14, 15]. Reactions of coor-
dinated isocyanides with polyfunctional nucleophiles
have been less studied, and their mechanism is more
complicated. For example, bis-isocyanide platinum(II)
complexes 1 react with such polynucleophiles as
aminoazaheterocycles to give initially monocarbene
complexes 2, and the latter are capable of undergoing
further transformations leading to deprotonated (3) or
even dinuclear structures (4, Scheme 1) [16–24].
Taking into account that the formation of dinuclear
carbene complexes 4 is a multistep process, it may be
presumed that such complexes containing different
isocyanide ligands could be synthesized by using in
Of particular interest are reactions with amino-
thiazaheterocycles, which provide analogous chemical
Scheme 1.
R
N
R
R
Cl
Cl
R
N
C
RNC
Cl
C N
HN
H
Pd
2
HN
Pd
Cl
Cl
N
C
N
CNR
Cl
CNR RNC
CNR
C
CNR
Cl
N
B
Pd
N
N
Pd
Pd
Pd
H
RNC
CNR
.
B HCl
−HCl
−
Cl
Cl
N
N
1
2
3
4
2
119

2
120
Cl
MIKHERDOV et al.
Scheme 2.
Cl–
Xyl
Xyl
N
Cl
XylNC
HN
C
Xyl
Xyl
C
N
Pd
CNXyl
CNXyl
XylNC
N
C
Xyl
N
CNXyl
5
(5 equiv)
1
Pd
HN
Pd
N
Pd
CHNXyl
C
CNXyl
Cl
.
Cl
CDCl
−25 HCl
3
Cl
N
Pd
+
Pd
o
N
2
0 C
S
Cl
Cl
N
N
1
6
S
S
8
7
the last stage a bis-isocyanide complex other than that
used in the first stage. However, examples of synthesis
of dinuclear carbene complexes from different iso-
cyanide complexes have not been reported so far.
Therefore, the goal of the present work was to explore
the possibility of synthesizing such compounds.
plexes 10 and 11 (Scheme 3). Presumably, the lower
basicity of nucleophile 9 is compensated by the higher
acidity of the corresponding monocarbene complex.
1
19
The product structure was determined by H and F
NMR spectroscopy (including COSY and NOESY
experiments), mass spectrometry in solution, and IR
spectroscopy in the solid state.
Initially, we examined the reaction of cis-dichloro-
bis(2,6-dimethylphenyl isocyanide)palladium(II) (1)
with 1,3-thiazol-2-amine (5). To achieve the above
goal, it was necessary to find conditions hampering
reaction of monocarbene intermediate with the second
isocyanide complex molecule. Unfortunately, even
when the reaction was carried out in chloroform at
room temperature with 5 equiv of the nucleophile in
the absence of a base, we obtained a mixture of
isomeric dinuclear complexes 7 and 8 instead of
expected monocarbene derivative 6 (Scheme 2) [21].
The rate of the reaction under study was lowered by
using analogous platinum(II) complexes instead of bis-
isocyanide palladium(II) complexes. Platinum(II)
complexes are more inert than their palladium analogs,
and they can be used to isolate and identify assumed
intermediates in reactions of coordinated isocyanides
with polyfunctional nucleophiles [16].
In fact, by reacting cis-dichlorobis(2,6-dimethyl-
phenyl isocyanide)platinum(II) (12) even with 2 equiv
of 5-(trifluoromethyl)-1,3,4-thiadiazol-2-amine (9) we
obtained neutral monocarbene complex 13 (Scheme 4)
Obviously, in this reaction the nucleophile also acts
as a base, and the resulting deprotonated form behaves
as nucleophile and attacks the second molecule of
complex 1, yielding dinuclear structures 7 and 8. Thus,
excess nucleophile favors not only formation of
monocarbene complex 6 but also its deprotonation.
1
19
195
whose structure was determined by H, F, and Pt
NMR spectroscopy, mass spectrometry in solution, and
IR spectroscopy (in the solid state).
No further reaction occurred when 1 equiv of 12 or
9
was added to complex 13. On the other hand, the
We then tried to use less basic 5-(trifluoromethyl)-
,3,4-thiadiazol-2-amine (9) instead of thiazole 5, but
the reaction of 9 with complex 1 under analogous con-
ditions also afforded only a mixture of dinuclear com-
addition of an equivalent amount of a base to a mixture
of equimolar amounts of 13 and 12 led to the forma-
tion of a mixture of isomeric dinuclear complexes 14
and 15 (Scheme 5) whose ratio depended on the
1
Scheme 3.
F3C
Xyl
N
S
Cl
XylNC
Xyl
Xyl
NH2
C
Pd
XylNC
N
C
Xyl
N
N
N
Pd
N
XylNC CNXyl
CNXyl
C
CNXyl
9
(5 equiv)
Cl
N
N
Pd
Pd
+
Pd
o
CDCl , 20 C
3
.
Cl
Cl
Cl
Cl
N
N
−
29 HCl
1
S
S
N
N
F3C
F3C
1
0
11
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 10 2018

FORMATION OF HOMO- AND HETERONUCLEAR PLATINUM(II) AND PALLADIUM(II)
2121
Scheme 4.
Xyl
S
N
N
F3C
F3C
2
N
S
o
Cl
Cl
C
C
CDCl , 20 C
3
N N
Cl
C NH
Pt
+
NH
2
.
N
−29 HCl
Pt
Xyl
N
C
N
Xyl
1
2
Xyl
9
13
temperature. At room temperature, the major product
was complex 14 (14:15 = 10:1) which was isolated in
the pure state by recrystallization. When an equimolar
mixture of 12, 13, and a base was heated under reflux,
the ratio 14:15 was 1:1.1. These findings suggest that
isomer 14 is a kinetically controlled product, and
isomer 15, thermodynamically controlled (as reported
previously for their palladium analogs [21].
In this case, the product ratio also depended on the
reaction conditions. The reaction at room temperature
afforded kinetically controlled isomer 16 as the major
product, the ratio 16:17 being 5:1. Under reflux
conditions, the amounts of isomers 16 and 17 were
1
95
approximately equal. In the Pt NMR spectra of 16
and 17 we observed only one platinum signal, and their
mass spectra showed isotope peaks typical of ions
containing both palladium and platinum atoms ([M –
The structure of complexes 14 and 15 was
+
+
1
95
Cl] , C39
H
36
N
7
F
3
SClPdPt ).
confirmed by NMR, IR, and mass spectra. The Pt
NMR spectra of both complexes displayed two signals
with equal intensities due to two nonequivalent
platinum centers.
In summary, we have studied reactions of cis-bis-
(
2,6-dimethylphenyl isocyanide) palladium(II) and
platinum(II) complexes {cis-[MCl (CNXyl) ]; M = Pd,
2
2
The isolation of monocarbene intermediate 13
opens the possibility of synthesizing new dinuclear
complexes. For example, the reaction of 13 with bis-
isocyanide palladium(II) complex 1 gave mixed
dinuclear complexes 16 and 17 containing different
metal centers, palladium and platinum (Scheme 6).
Pt; Xyl = 2,6-Me C H } with weakly nucleophilic 5-(tri-
2 6 3
fluoromethyl)-1,3,4-thiadiazol-2-amine. In the reaction
with the palladium-coordinated bis-isocyanide, this
nucleophile behaves similarly to more nucleophilic
thiazole-2-amines, giving rise to isomeric dinuclear
complexes. Excess 5-(trifluoromethyl)-1,3,4-thiadiazol-
Scheme 5.
Xyl
N
C
C
Cl
Xyl
S
Pt
F3C
N
N
Y N
Cl
C N
Xyl
Xyl
Pt
N
N
Xyl
Cl
Cl
C
C
C
N
Pt
S
14
S
Xyl
F3C
F3C
N
N
1
2
B
−
+
Xyl
Xyl
N N
Cl
C NH
C N
N N
Cl
Pt
Pt
Xyl
Xyl
CHCl
3
N
N
C
C
N
C C
Pt
N
S
F3C
Xyl
N
1
3
Xyl
Cl
Y N
Cl
C N
Pt
Xyl
C
N
15
Xyl
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 10 2018

2
122
MIKHERDOV et al.
Scheme 6.
Xyl
N
C
Cl
Xyl
S
Pd
N
F3C
N
C
Y N
Cl
C N
Xyl
Xyl
Pt
N
N
Xyl
Cl
C
C
C
N
Pd
Cl
S
S
Xyl
F3C
F3C
16
N
N
B
−
1
N N
Cl
C NH
N N
Cl
C N
Pt
Pt
+
Xyl
Xyl
CHCl3
Xyl
Cl
C
C
Xyl
N
N
N
N
C
Xyl
Xyl
1
3
C
S
F3C
Pd
N
Y N
Cl
C N
Pt
Xyl
C
N
Xyl
1
7
2
-amine reacts with cis-dichlorobis(2,6-dimethylphenyl
refluxed for 30 min with stirring, cooled to room
temperature, and evaporated to a volume of 2 mL. The
product was precipitated with hexane (10 mL),
separated by centrifugation, washed with hexane
(2×10 mL), and air-dried. Yield 0.89 g (88%). IR
isocyanide)platinum(II) to give monocarbene complex
which undergoes deprotonation in the presence of the
organic base and acts as nucleophile toward bis-
isocyanide palladium(II) and platinum(II) complexes;
as a result homo- and heteronuclear isocyanide/carbene
complexes are formed.
–
1
1
spectrum, ν, cm : 2229, 2212 s (C≡N). H NMR
spectrum, δ, ppm (J, Hz): 2.52 s (12H, CH ), 7.20 d
3
(
4H, m-H, J = 7.8), 7.35 t (2H, p-H, J = 7.8). The
EXPERIMENTAL
spectral parameters of 1 coincided with those reported
Unless otherwise stated, organic and inorganic
reagents and solvents were commercial products
in [21].
cis-[PtCl (CNXyl) ] (12) was synthesized in a
similar way from 0.5 g (1.33 mmol) PtCl (NCEt) and
2
2
(
Aldrich) used without additional purification.
2
2
The IR spectra were recorded on a Shimadzu IR
0
.38 g (2.66 mmol) of 2,6-dimethylphenyl isocyanide.
–
1
–
1
Affinity spectrometer (4000–400 cm ) from samples
prepared as KBr discs. The mass spectra were obtained
on a Bruker micrOTOF spectrometer (electrospray
Yield 625 mg (89%). IR spectrum, ν, cm : 2229, 2201
s (C≡N). H NMR spectrum, δ, ppm (J, Hz): 2.51 s
1
(
12H, CH ), 7.19 d (4H, m-H, J = 7.6), 7.34 t (2H,
3
195
ionization; solvent MeOH or MeOH–CH Cl ; a.m.u.
2
2
p-H, J = 7.6). Pt NMR spectrum: δ –3753 ppm,
quint (J = 105.0 Hz). The spectral parameters of 12
coincided with those reported in [29].
Pt
range 50–3000 Da); m/z values are given for most
1
19
195
abundant isotopes. The H, F, and Pt NMR spectra
were measured on a Bruker Avance spectrometer
1
Dinuclear complexes 10 and 11. A suspension of
complex 1 (24 mg, 0.055 mmol) in 5 mL of CH Cl
(
400 MHz for H) at room temperature using CDCl as
3
2
2
solvent.
was added to solid 5-(trifluoromethyl)-1,3,4-thiadiazol-
2-amine (9) (14 mg, 0.083 mmol), and the mixture was
stirred for 24 h at room temperature. The mixture was
filtered from 5-(trifluoromethyl)-1,3,4-thiadiazol-2-
amine hydrochloride, and the filtrate was evaporated
cis-[PdCl (CNXyl) ] (1). Solid 2,6-dimethylphenyl
2
2
isocyanide, 0.5 g (3.8 mmol), was added to a
suspension of 0.5 g (1.9 mmol) of PdCl (NCMe) in
2
2
1
0 mL of 1,2-dichloroethane. The mixture was
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 10 2018

FORMATION OF HOMO- AND HETERONUCLEAR PLATINUM(II) AND PALLADIUM(II)
2123
under reduced pressure at room temperature. Yield
5 mg (94%), isomer ratio 10:11 = 1:1.1. IR spectrum,
6.61 d (2H, m-H, J = 7.5), 6.90 d (2H, m-H, J = 7.6),
2
6.97 d (2H, m-H, J = 7.6), 7.05 d (2H, m-H, J = 7.6),
–
1
19
ν, cm : 2964, 2904 s (C–H), 2211, 2206 s (C≡N),
638, 1620, 1559, 1490 s (N=C), 798, 773 br [δ(C–H)].
7.12 t (1H, p-H, J = 7.6), 7.18 t (1H, p-H, J = 7.6). F
1
95
1
NMR spectrum: δ –60.04 ppm. Pt NMR spectrum,
F
1
H NMR spectrum, δ, ppm (J, Hz): 2.19 s (6H, CH3,
0), 2.23 s (6H, CH , 11), 2.25 s (6H, CH , 10), 2.27 s
δ , ppm: −3844.05, −3790.60. Mass spectrum: m/z
Pt
+
+
1
1117.1680 [M – Cl] (calculated for C H N F SClPt :
3
3
39 36 7 3 2
(
1
7
6H, CH , 11), 2.28 s (6H, CH , 10), 2.30 s (6H, CH ,
1117.1691).
3
3
3
1), 2.44 s (6H, CH , 10 + 11), 6.18 t (1H, p-H, J =
1
3
Complex 15. H NMR spectrum, δ, ppm (J, Hz):
.5, 10), 6.31 t (1H, p-H, J = 7.5, 11), 6.39 t (1H, p-H,
2
2
.21 s (6H, CH ), 2.26 s (6H, CH ), 2.29 s (6H, CH ),
.41 s (6H, CH ), 6.22 t (1H, p-H, J = 7.5), 6.34 t (1H,
3
3
3
J = 7.5, 11), 6.51 t (1H, p-H, J = 7.5, 10), 6.68 d (2H,
m-H, J = 7.5, 10), 6.83 d (2H, m-H, J = 7.5, 11), 6.88 d
3
p-H, J = 7.6), 6.77 d (2H, m-H, J = 7.5), 6.87 d (2H,
m-H, J = 7.6), 6.96 d (2H, m-H, J = 7.6), 7.05 d (2H,
m-H, J = 7.6), 7.12 t (1H, p-H, J = 7.6), 7.19 t (1H,
p-H, J = 7.6). F NMR spectrum: δ −59.57 ppm. Pt
NMR spectrum, δ , ppm: −3801.55, −3747.25.
(
2H, m-H, J = 7.5, 11), 6.93 d (2H, m-H, J = 7.5, 10),
.99 d (2H, m-H, J = 7.5, 10 + 11), 7.07 d (2H, m-H,
J = 7.5, 10 + 11), 7.16 t (1H, p-H, J = 7.5, 10 + 11),
6
19
195
F
1
9
7
.27–7.19 m (1H, p-H, J = 7.5, 10 + 11). F NMR
Pt
spectrum, δ , ppm: –59.42 (11), –59.98 (10). Mass spec-
trum: m/z 940.0475 [M – Cl] (calculated for
C H ClF N Pd S : 940.0462).
F
+
Heteronuclear complexes 16 and 17. A solution of
complex 13 (15 mg, 0.023 mmol) in 5 mL of CHCl3
was added to a mixture of PdCl (CNXyl) (1) (12 mg,
+
3
9
36
3
7
2
2
2
Complex 13 was synthesized in a similar way from
5 mg (0.151 mmol) of 5-(trifluoromethyl)-1,3,4-
0
.023 mmol) and tribenzylamine (7 mg, 0.024 mmol).
2
The mixture was stirred for 24 h at room temperature
and evaporated under reduced pressure to a volume of
thiadiazol-2-amine (9) and 40 mg (0.075 mmol) of
PtCl (CNXyl) (12). Yield 40 mg (80%). IR spectrum,
ν, cm : 2958 s (C–H), 2229 s (C≡N), 1638, 1635,
2
2
2
mL, and 2 mL of diethyl ether was added. The
–
1
products were isolated by crystallization upon slow
evaporation of the solution at room temperature.
Complexes 16 and 17 were isolated as a 2:1 mixture;
1
1
500, 14510 s (N=C), 775 br [δ(C–H)]. H NMR
spectrum, δ, ppm (J, Hz): 2.25 s (6H, CH ), 2.47 s (6H,
CH ), 6.52 t (1H, p-H, J = 7.6), 6.68 d (2H, m-H, J =
7
7
7
NMR spectrum: δ –59.71 ppm. Pt NMR spectrum:
δ –3862.59 ppm. Mass spectrum: m/z 661.0723 [M +
H] (calculated for C H ClF N PtS : 661.0718).
3
1
3
yield 18 mg (74%). H NMR spectrum, δ, ppm (J, Hz):
.6), 6.83 d (2H, m-H, J = 7.6), 6.90 d (2H, m-H, J =
.6), 6.93 d (2H, m-H, J = 7.6), 7.07 d (2H, m-H, J =
2
.07 s (6H, CH , 16), 2.23 s (6H, CH , 17), 2.26 s (6H,
3 3
CH , 16), 2.28 s (6H, CH , 17), 2.29 s (6H, CH , 16),
3
3
3
19
.6), 7.24 t (1H, p-H, J = 7.6), 8.15 br.s (1H, NH). F
2
.31 s (6H, CH , 17), 2.44 s (6H, CH , 16), 2.45 s (6H,
3
3
1
95
F
CH , 17), 6.18 t (1H, p-H, J = 7.5, 16), 6.31 t (1H,
3
Pt
p-H, J = 7.5, 17), 6.36 t (1H, p-H, J = 7.5, 17), 6.47 t
+
+
2
1
20
3
5
(
1H, p-H, J = 7.5, 16), 6.68 d (2H, m-H, J = 7.5, 16),
Dinuclear complexes 14 and 15. A solution of
complex 13 (15 mg, 0.023 mmol) in 5 mL of CHCl3
was added to a mixture of PtCl (CNXyl) (12) (12 mg,
6.83 d (2H, m-H, J = 7.5, 17), 6.86 d (2H, m-H, J =
7.5, 17), 6.93 d (2H, m-H, J = 7.5, 16), 6.99 d (2H, m-
H, J = 7.5, 17), 7.00 d (2H, m-H, J = 7.5, 16), 7.06 d
(2H, m-H, J = 7.5, 17), 7.07 d (2H, m-H, J = 7.5, 16),
7.15 t (1H, p-H, J = 7.5, 16 + 17), 7.27–7.19 m (1H,
2
2
0
.023 mmol) and tribenzylamine (7 mg, 0.024 mmol).
The mixture was stirred for 24 h at room temperature
to obtain complex 14) or under reflux (to obtain a
1
9
(
p-H, J = 7.5, 16 + 17). F NMR spectrum, δ , ppm:
F
195
mixture of 14 and 15). It was then evaporated under
reduced pressure to a volume of 2 mL, and 2 mL of
diethyl ether was added. The products were isolated by
crystallization upon slow evaporation of the solution at
room temperature. Yield of pure complex 14 11 mg
–60.09 (16), –59.52 (15). Pt NMR spectrum, δPt,
ppm: –3797.35 (16), –3755.40 (17). Mass spectrum:
+
m/z 1027.1112 [M
–
Cl]
(calculated for
+
C H N F SClPdPt : 1027.1076).
3
9
36
7 3
(
42%). Complex 15 was isolated in a mixture with
ACKNOWLEDGMENTS
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 18-03-00119, synthesis and structure of carbene
palladium complexes; project no. 18-33-00704mol_a,
synthesis and structure of carbene platinum
complexes) using the facilities of the Magnetic
isomer 14 (2:1); yield 19 mg (73%).
–
1
Complex 14. IR spectrum, ν, cm : 2954 s (C–H),
2
228 s (C≡N), 1638, 1500, 1410 s (N=C), 775 br [δ(C–H)].
1
H NMR spectrum, δ, ppm (J, Hz): 2.06 s (6H, CH3),
2
6
.24 s (6H, CH ), 2.27 s (6H, CH ), 2.42 s (6H, CH ),
3 3 3
.08 t (1H, p-H, J = 7.5), 6.44 t (1H, p-H, J = 7.6),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 10 2018

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MIKHERDOV et al.
Resonance Research Center, Chemical Analysis and
Materials Research Center, and Chemistry Educational
Center of the St. Petersburg State University.
and Bochmann, M., Dalton Trans., 2017, vol. 46,
p. 13397. doi 10.1039/C7DT02804K
5. Bertrand, B., Romanov, A.S., Brooks, M., Davis, J.,
Schmidt, C., Ott, I., O’Connell, M., and Bochmann, M.,
Dalton Trans., 2017, vol. 46, no. 45, p. 15875. doi
1
CONFLICT OF INTERESTS
No conflict of interests was declared by the authors.
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