Iridium complexes with 2,1,3-benzothiadiazole and related ligands

Article abstract of DOI:10.1016/j.poly.2012.05.015

The reaction of [IrCp*Cl(μ-Cl)]₂ (5) with 2,1,3-benzothiadiazole (1) in a 1:1 ratio gives the binuclear complex [Ir ₂Cp*₂Cl₄(μ, η²-1)] (6) where 1 acts as a bridging ligand. The 4-XH derivatives of 1 (2, X = O; 3, X = NH) interacted with 5 in various ways. Under basic conditions, 2 and 5 form chelate complexes [IrCp*ClL] (7) (L = C₆H₃ON ₂S) (isolated in the form of a co-crystal with the initial 2 and in the individual form, in both cases with solvated toluene) or [Ir ₂Cp*₂Cl₃(μ, η³-L)] (8) in the 4:1, 2:1 or 1:1 reactions, respectively. Derivative 3, even with an excess of 5, affords only the mononuclear complex [IrCp*Cl₂(3)] (9) where 3 acts as a monodentate ligand, bonded to the Ir center by the ring N atom. A similar complex, [IrCp*Cl₂(4)] (10), was also obtained from 5 and acenaphtho[1,2-c][1,2,5]thiadiazole (4) in excess of the former reagent. The structures of complexes 6-10 were confirmed by single-crystal X-ray diffraction.

Full text of DOI:10.1016/j.poly.2012.05.015

Polyhedron 42 (2012) 168–174
Contents lists available at SciVerse ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Iridium complexes with 2,1,3-benzothiadiazole and related ligands
Denis A. Bashirov a,b, Taisiya S. Sukhikh a, Natalia V. Kuratieva a,b, Dmitry Yu. Naumov a,
c
c,d,
Sergey N. Konchenko a,b, , Nikolay A. Semenov , Andrey V. Zibarev
⇑
⇑
a Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, 630090 Novosibirsk, Russia
b Department of Natural Sciences, National Research University – Novosibirsk State University, 630090 Novosibirsk, Russia
c Vorozhtsov Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, 630090 Novosibirsk, Russia
d Department of Physics, National Research University – Novosibirsk State University, 630090 Novosibirsk, Russia
a r t i c l e i n f o
a b s t r a c t
Article history:
The reaction of [IrCp*Cl(l-Cl)]2 (5) with 2,1,3-benzothiadiazole (1) in a 1:1 ratio gives the binuclear com-
plex [Ir2Cp*2Cl4(l, g
2-1)] (6) where 1 acts as a bridging ligand. The 4-XH derivatives of 1 (2, X = O; 3,
Received 24 November 2011
Accepted 14 May 2012
Available online 28 May 2012
X = NH) interacted with 5 in various ways. Under basic conditions, 2 and 5 form chelate complexes
[IrCp*ClL] (7) (L = C6H3ON2S) (isolated in the form of a co-crystal with the initial 2 and in the individual
form, in both cases with solvated toluene) or [Ir2Cp*2Cl3(l, g
3-L)] (8) in the 4:1, 2:1 or 1:1 reactions,
respectively. Derivative 3, even with an excess of 5, affords only the mononuclear complex [IrCp*Cl2(3)]
(9) where 3 acts as a monodentate ligand, bonded to the Ir center by the ring N atom. A similar complex,
[IrCp*Cl2(4)] (10), was also obtained from 5 and acenaphtho[1,2-c][1,2,5]thiadiazole (4) in excess of the
former reagent. The structures of complexes 6–10 were confirmed by single-crystal X-ray diffraction.
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction
Recently, it was also found that radical anions (RAs) of 2,1,3-
benzothiadiazole derivatives [25], isolated in the form of stable
In recent years, heterocyclic, coordination and, especially, mate-
rials chemistry of 2,1,3-benzothiadiazole derivatives (known since
the 19th century) have received much attention, in part due to their
redox properties [1]. Particularly, these derivatives were used as
components of organic light-emitted diodes (OLEDs) and low-band
gap polymers for photovoltaic applications [2–9]. For OLED applica-
tions, the compounds under discussion are promising not only as
structural units of polymers but also as ligands in transition metal
complexes [2]. However, only a limited number of complexes,
including those of Ag, Cd, Co, Cu, Hg, Pd and Ru, were unambigu-
ously structurally characterized for the archetypal 2,1,3-benzothia-
diazole (1) and its functional derivatives bearing, for example, 4-XH
(X = O, NH; 2 and 3, respectively) groups [2,10–18]. Some other rel-
evant complexes, for example, [MCl(Tol)(CO)(PPh3)2(1)] (M = Ru,
Os; Tol = toluene) and [IrCl2H(PPh3)2(1)], were characterized only
spectroscopically [19].
salts with metal cations, for example, [K(18-crown-6)]+[1]ꢀꢀ [26],
are of interest as components of molecular magnets [27] (para-
magnetic mono- and binuclear complexes formed by the RA of 1
with carbonyls of Cr, Mo and W were identified in solution by
EPR a quarter of century ago [28]). One of new approaches to such
salts might be the coordination of the neutral 2,1,3-benzothiadiaz-
ole molecule to a metal center, followed by reduction into the RA.
In this work, which is part of a broader project aimed at the
preparation of 2,1,3-benzodithiazolidyl salts with transition metal
cations [27], we describe new coordination iridium compounds ob-
tained by the interaction of 1–3 and the related acenaphtho[1,2-
c][1,2,5]thiadiazole (4) with [IrCp*Cl(l -Cl)]2 (5).
2. Results and discussion
It has been found that the 1:1 reaction between 1 and 5 gives
Amongst the transition metals, one of the most promising in the
context of OLEDs is iridium [20–24]. In the field, however, iridium
complexes of 2,1,3-benzothiadiazole belong to the group of rela-
tively poorly studied compounds [24].
the binuclear complex [Ir2Cp*2Cl4(
l
,
g
2-1)] (6) (ꢁ83%), in which
1 acts as a bridging ligand connecting two Ir centers (Scheme 1).
The structure of 6 was confirmed by single crystal X-ray diffraction
(XRD; Fig. 1).
In complex 6 (Fig. 1), the ligand 1 lies at the 2 site symmetry po-
sition, passing through the S atom and the middle point of the C1–
C10 bond. The Ir atoms deviate from the molecular plane of 1, and
the Cp* rings are located on the opposite sides of this plane.
Compound 2 is a weak acid and can react as a neutral molecule
or as an O-anion [10,11]. In order to substitute chloride ligands at
⇑
Corresponding authors. Addresses: Nikolaev Institute of Inorganic Chemistry,
SB RAS, prosp. Lavrentiev 3, 630090, Russia (S.N. Konchenko), Vorozhtsov Institute
of Organic Chemistry, SB RAS, prosp. Lavrentiev 9, 630090, Russia (A.V. Zibarev).
E-mail addresses: snkonch@googlemail.com (S.N. Konchenko), zibarev@nioch.
nsc.ru (A.V. Zibarev).
0277-5387/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2012.05.015

D.A. Bashirov et al. / Polyhedron 42 (2012) 168–174
169
N
Cl
Ir
Cl
S
+
[IrCp*Cl(µ-Cl)]2
N
Ir
N
N
Cl
S
Cl
1
5
6
Scheme 1. The reaction of 5 with 1.
Cl2
Error
C1
C1'
N1
N1'
Ir1
Ir1'
Cl1
S1
Cl2'
Error
Cl1'
Fig. 1. Crystal structure fragment of complex 6 (H atoms omitted), selected bond lengths (Å) and angles (°): Ir1–N1 2.111(2), Ir1–Cl1 2.4097(6), Ir1–Cl2 2.3908(7), S1–N1
1.644(2), N1–C1 1.351(3), C1–C10 1.428(5); Cl1–Ir1–Cl2 88.41(2), Cl1–Ir1–N1, 83.69(6), Cl2–Ir1–N1 87.34(6).
the Ir centers, its reactions with 5 were performed under basic con-
ditions with an excess of K2CO3. Depending upon the molar ratio of
the reagents, two different complexes were obtained (Scheme 2).
With compounds 2 and 5 in a 4:1 molar ratio, the complex
[IrCp*ClL] (7; L = C6H3ON2S) was isolated (80%) in the toluene sol-
vated form, co-crystallized with the initial compound 2 (Fig. 2). In
this complex, the heterocyclic ligand chelates to the Ir center by
practically in the heterocycle molecular plane, while the Cp* rings
are located on opposite sides of this plane. The Ir–O bond distances
in 7 and 8 are expectedly shorter than in the co-crystal of 7 with 2
(Fig. 2).
The reaction between 5 and 3, where 3 is a weak base, was per-
formed under neutral conditions and with a reagents molar ratio of
1:1 to avoid the formation of a mixture of products. The mononu-
clear complex [IrCp*Cl2(3)] (9) (Scheme 3) was isolated. The same
product was also obtained with an excess of 5. For complex 9 one
might expect two types of ligand coordination, involving the NH2
group and/or the heterocyclic N atom, which is known for Cd(II)
[12] and Cu(I) [13] compounds. However, only the latter type is ob-
served for 9, where a molecule of 3 acts as a monodentate ligand
coordinated to the Ir center by the ring N atom (Fig. 4).
In the case of 4 (a non-functionalized heterocycle related to 1),
the mononuclear complex [IrCp*Cl2(4)] (10) was synthesized via
its 1:1 reaction with 5 (Scheme 4). The complex 10 was isolated
as a solvate with CH2Cl2. The same complex was also obtained with
an excess of 5. Structurally, complex 10 (Fig. 5) is similar to com-
plex 9 (Fig. 4).
its O and N atoms. The molecule of 2 is involved in p-stacking inter-
actions with the Cp* group of one Cp*Ir moiety (interplanar distance
3.50 Å), and in an OHꢂ ꢂ ꢂO hydrogen bond with the chelating ligand
at another Cp*Ir moiety (O24ꢂ ꢂ ꢂO34, 2.654(2) Å). The 1H NMR spec-
trum of 7 in chloroform does not reveal the signal of the OH group.
This indicates that the hydrogen bond also exists in solution.
With compounds 2 and 5 in a 2:1 molar ratio, the toluene sol-
vate of individual 7 was isolated as the major product (55%) to-
gether with the complex [Ir2Cp*2Cl3(l, g
3-L)] (8, Scheme 2;
L = C6H3ON2S) as the minor product (7%). With a 1:1 ratio, complex
8 was obtained as the main product (45%). According to the XRD
data, the individual complex 7 (Fig. 2) and complex 8 (Fig. 3) pos-
sess common structural features. One can see that the binuclear
complex 8 is formed via coordination of complex 7 by the second
heterocyclic N atom to a IrCp*Cl2 moiety. The two Ir atoms lie
In complex 10 (Fig. 5), the heterocyclic ligand is coordinated
with only one IrCp*Cl2 moiety, which most likely reflects its
N
O
O
K2CO3
S
Cl
+
[IrCp*Cl(µ-Cl)]2
+
CH2Cl2
N
Ir
N
Ir
N
N
Ir
N
Cl
S
Cl
Cl
S
OH
5
2
8
7
Scheme 2. The reaction of 5 with 2.

170
D.A. Bashirov et al. / Polyhedron 42 (2012) 168–174
Ir1
N23
O24
S22
O34
N33
C23A
C27A
C34
C24
S32
N22
C33A
Cl1
C37A
N31
S2
Cl1
N1
C7A
N3
C3A
C4
Ir1
Error
O4
Fig. 2. Crystal structure fragment of complex 7 (H atoms omitted). Top: toluene solvate of co-crystal with 2, selected bond lengths (Å) and angles (°): Ir1–N23 2.107(3), Ir1–
O24 2.168(4), Ir1–Cl1 2.3917(11), S22–N23, 1.640(3), S22–N22 1.612(4), S32–N33 1.624(4), S32–N31 1.610(5), N23–C23A 1.344(5), N22–C27A 1.359(6), N33–C33A 1.337(6),
N31–C37A 1.434(6), C23A–C27A 1.417(5), C33A–C37A 1.434(6), O24–C24 1.326(6), O34–C34 1.359(5); Cl1–Ir1–O24 87.08(12), Cl1–Ir1–N23 84.71(10), O24–Ir–N23
77.93(14), O24–C24–C23A 116.1(4), O34–C34–C33A 115.9(4). Bottom: toluene solvate of 7 (space-filling toluene molecule omitted), selected bond lengths (Å) and angles (°):
Ir1–N3 2.116(4), Ir1–O4 2.146(3), Ir1–Cl1 2.3995(11), S2–N3 1.633(4), S2–N1 1.635(4), N3–C3A 1.345(5), N1–C7A 1.346(6), C3A–C7A 1.418(6), O4–C4 1.308(6); Cl1–Ir1–O4
85.96(8), Cl1–Ir1–N3 86.21(10), O4–Ir1–N3 78.15(13), O4–C4–C3A 117.3(4).
sterical hindrance. The Ir atom lies practically in the molecular
plane of the heterocycle.
A common structural feature of complexes 6–10 is that the Ir
centers reveal a pseudo-octahedral coordination pattern (‘‘piano
stool’’), with three coordination positions within the same octahe-
dral face occupied by the Cp* ring.
1H and 13C NMR spectra were measured for solutions in chloro-
form-d with a Bruker DRX-500 instrument, at a frequency of
500.13 MHz (1H) and 125.76 MHz (13C) by using the solvent
(dH = 7.24, dC = 77.23) signal as an inner standard. A 1H–13C heter-
onuclear single quantum correlation spectrum was recorded for 7.
3.2. X-ray diffraction analysis
3. Experimental
The single-crystal data (Table 1) were collected with a Bruker-
3.1. General
Nonius X8Apex diffractometer at 150 K using Mo K
(k = 0.71073 Å) with a graphite monochromator. The
a
irradiation
-scans of
u
All preparations were performed under an argon atmosphere
using standard glove-box and Schlenk techniques. The solvents
were dried by common drying agents and redistilled under argon.
In all syntheses, the reaction solvents were distilled off under re-
duced pressure. Potassium carbonate was calcinated (10 h at
150 °C) directly before use. Compounds 1 [29], 2 [30], 3 [31], 5
[32] and SCl2 [32] were synthesized by known methods.
narrow (0.5°) frames were used. The absorption corrections were
made semi-empirically with the SADABS program [33]. The struc-
tures were solved by Direct methods using the program SHELXS-97
[34]. The refinement and all further calculations were carried out
using SHELXL-97 [34]. The non-H atoms were refined anisotropically,
using weighted full-matrix least-squares on F2. The C-bound H-
atoms were included in calculated positions and treated as riding

D.A. Bashirov et al. / Polyhedron 42 (2012) 168–174
171
Cl2
C4
O4
Error
C3A
S2
C7A
Ir2
Cl1
Ir1
N3
N1
Error
Cl3
Fig. 3. Crystal structure fragment of complex 8 (H atoms omitted), selected bond lengths (Å) and angles (°): Ir2–N3 2.112(3), Ir2–O4 2.134(2), Ir2–Cl3 2.3862(9), Ir1–N1
2.114(3), Ir1–Cl1 2.4128(9), Ir1–Cl2 2.4015(9), S2–N1 1.667(3), S2–N3 1.644(3), N1–C7A 1.355(4), N3–C3A 1.331(4), C3A–C7A 1.416(5), O4–C4 1.304(4); Cl3–Ir2–O4
87.54(7), Cl3–Ir2–N3 84.07(8), O4–Ir2–N3 77.87(10), Cl1–Ir1–Cl2 88.30(3), Cl1–Ir1–N1 82.82(8), Cl2–Ir1–N1 86.08(8), O4–C4–C3A 116.9(3).
NH2
N
Cl
Ir
S
+
[IrCp*Cl(µ-Cl)]2
N
N
N
S
Cl
NH2
5
3
9
Scheme 3. The reaction of 5 with 3.
atoms using SHELXL default parameters. In 7–2 the toluene solvent
molecules suffer from high thermal disorder. In complexes 7 and
10 the hydrogen atoms on the disordered solvent molecules, tolu-
ene and dichloromethane, respectively, were not included in the
refinement.
S2
N3
Cl2
C3A
N4
N1
C4
Error
3.3. Syntheses
C7A
Ir1
Complex 6: A solution of 0.010 g (0.073 mmol) of 1 and 0.059 g
(0.074 mmol) of 5 in 10 mL of toluene was stirred and heated at
80 °C for 3 h. The solvent was distilled off, and the residue was ex-
tracted with 6 mL of CH2Cl2. After filtration of the solution, 6 mL of
hexane were layered onto it, and the two-layer system was left at
ambient temperature until diffusion of the solvents ceased. Com-
plex 6 was obtained in the form of dark-red crystals suitable for
XRD, 0.056 g (ꢁ80%). Found (%): C, 33.5; H, 3.7; N, 3.1. Calculated
for C26H34Cl4Ir2N2S (%): C, 33.47; H, 3.67; N, 3.00. 1H NMR (d):
Cl1
Fig. 4. Crystal structure fragment of complex 9 (H atoms omitted), selected bond
lengths (Å) and angles (°): Ir1–N1 2.108(2), Ir1–Cl1 2.4151(7), Ir1–Cl2 2.4096(7),
S2–N1 1.644(2), S2–N3 1.612(2), N1–C7A, 1.352(3), N3–C3A 1.349(3), C3A–C7A
1.424(3), N4–C4 1.374(3); Cl1–Ir1–Cl2 89.42(2), Cl1–Ir1–N1 86.90(6), Cl2–Ir1–N1
83.50(6), N4–C4–C3A 120.4(2).
S
N
S
N
N
Cl
N
Ir
[IrCp*Cl(µ-Cl)]2
+
Cl
5
4
10
Scheme 4. The reaction of 5 with 4.

172
D.A. Bashirov et al. / Polyhedron 42 (2012) 168–174
toluene, and the solution was concentrated to a volume of ca.
N1
5 mL and left to stand at ꢀ25 °C. Complex 7 (co-crystal with 2, tol-
uene solvate) was obtained in the form of dark-red crystals suitable
for XRD, 0.077 g (ꢁ80%). Found (%): C, 46.3; H, 3.9; N, 7.2. Calculated
for C29H30ClIrN4O2S2 (%): C, 45.93; H, 3.99; N, 7.39. 1H NMR (d):
7.47–7.54 (m, 3H, het. ligand and 2), 7.25 (m, toluene), 7.17 (m, tol-
uene), 6.97 (dd, 1H, 2), 6.83 (d, 1H, het. ligand), 6.54 (d, 1H, het. li-
gand), 2.34 (s, toluene), 1.79 (s, 15H, Cp*). 13C NMR (d): 163.46 (s),
158.43 (s), 155.85 (s), 137.46 (s), 110.88 (s), 105.61 (s, C, het. ligand)
156.12 (s), 147.83 (s), 147.77 (s), 131.40 (s), 113.42 (s), 110.44 (s, C,
2), 86.04 (s, C5(CH3)5), 9.69 (s, C5(CH3)5), 138.05 (s), 129.21 (s),
128.40 (s), 125.47 (s), 21.63 (s, toluene).
S2
C9B
C3A
Cl2
N3
Ir1
Error
Complex 7 (toluene solvate): A mixture of 0.115 g (0.144 mmol)
of 5, 0.044 g (0.289 mmol) of 2 and 0.135 g (0.978 mmol) of K2CO3
in 15 mL of CH2Cl2 was worked-up as described above. Complex 7
(toluene solvate) was obtained in the form of dark-red crystals
suitable for XRD, 0.044 g (ꢁ55%). Found (%): C, 41.6; H, 3.9; N,
4.9. Calculated for C19.5H22ClIrN2OS (%): C, 41.81; H, 3.95; N, 5.00.
1H NMR (d): 7.51 (dd, 1H, het. ligand), 7.25 (m, toluene), 7.17 (m,
toluene), 6.83 (d, 1H, het. ligand), 6.54 (d, 1H, het. ligand), 2.35
(s, toluene), 1.78 (s, 15H, Cp*). 13C NMR (d): 163.77 (s), 158.51
(s), 155.79 (s, C3a, C4, C7a), 137.49 (s), 110.73 (s), 105.28 (s, CH,
het. ligand), 85.95 (s, C5(CH3)5), 9.66 (s, C5(CH3)5), 138.05 (s),
129.21 (s), 128.40 (s), 125.47 (s), 21.63 (s, toluene).
Cl1
Fig. 5. Crystal structure fragment of complex 10 (H atoms of the ligands and solvate
molecule CH2Cl2 omitted), selected bond lengths (Å) and angles (°): Ir1–N3
2.119(2), Ir1–Cl1 2.4018(6), Ir1–Cl2 2.4159(6), S2–N3 1.686(2), S2–N1 1.639(3),
N3–C3A 1.317(3), N1–C9B 1.315(4), C3A–C9B 1.442(3); Cl1–Ir1–Cl2 89.09(2), Cl1–
Ir1–N3 87.36(6), Cl2–Ir1–N3 85.16(6).
8.07 (dd, 2H, het. ligand), 7.61 (dd, 2H, het. ligand), 1.57 (s, 15H,
Cp*). 13C NMR (d): 154.84 (s), 130.45 (s), 121.96 (s, C, het. ligand),
86.79 (s, C5(CH3)5), 9.44 (s, C5(CH3)5).
As a toluene-insoluble minor by-product (ꢁ7%), complex 8 (see
below) was identified.
Complex 8: A mixture of 0.232 g (0.289 mmol) of 5, 0.044 g
(0.289 mmol) of 2 and 0.135 g (0.978 mmol) of K2CO3 in 15 mL of
CH2Cl2 was stirred for 24 h at ambient temperature. The solution
was evaporated to dryness and the residue washed with 10 mL
of toluene and extracted with 10 mL of CH2Cl2. The extract was
concentrated to a volume of ca. 3 mL, and 5 mL of hexane were
Complex 7 (co-crystal with 2, toluene solvate): A mixture of
0.101 g (0.127 mmol) of 5, 0.077 g (0.507 mmol) of 2 and 0.144 g
(1.043 mmol) of K2CO3 in 15 mL of CH2Cl2 was stirred for 24 h at
ambient temperature. The purple solution was filtered (the solid
on the filter was washed twice with 3 mL of CH2Cl2), and the
solvent was distilled off. The residue was extracted with 10 mL of
Table 1
Crystallographic data for complexes.
Complex
6
7ꢂ2ꢂToluene
7ꢂ0.5Toluene
8
9
10ꢂ0.5CH2Cl2
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
C26H34Cl4Ir2N2S
932.81
monoclinic
C 2/c
13.6692(3)
9.1009(2)
23.2119(6)
90
94.807(1)
90
2877.45(12)
4
2.153
1768
9.704
C29H30ClIrN4O2S2
758.34
monoclinic
Cc
C19.5H22ClIrN2OS
560.10
C26H33Cl3Ir2N2OS
912.35
monoclinic
P21/c
21.7315(6)
7.6226(2)
17.5051(5)
90
100.858(1)
90
2847.82(14)
4
2.128
1728
9.714
C16H20Cl2IrN3S
549.51
orthorhombic
Pbca
C22.5H22Cl3IrN2S
651.03
monoclinic
P21/n
9.1774(1)
15.5248(2)
15.6690(2)
90
102.213(1)
90
2181.95(5)
4
1.982
1260
6.596
triclinic
ꢀ
P1
8.1288(2)
26.2180(6)
14.0695(3)
90
102.557(1)
90
2926.78(12)
4
1.721
8.0709(2)
9.5676(3)
13.3644(4)
102.506(2)
106.867(2)
95.559(1)
949.97(5)
2
13.6129(2)
14.3948(2)
18.4086(3)
90
90
90
3607.26
8
2.024
2112
7.816
b (Å)
c (Å)
a
(°)
b (°)
c
(°)
V (Å3)
Z
Dcalc (g cmꢀ3
F(000)
)
1.958
542
7.289
1496
4.830
l
(mmꢀ1
)
Crystal size (mm)
2hmax (°)
0.40 ꢃ 0.40 ꢃ 0.35
0.11 ꢃ 0.10 ꢃ 0.08
0.32 ꢃ 0.26 ꢃ 0.22
0.30 ꢃ 0.05 ꢃ 0.01
0.16 ꢃ 0.12 ꢃ 0.05
0.22 ꢃ 0.09 ꢃ 0.05
61.00
56.66
56.46
61.18
56.56
65.28
Index range
ꢀ19 6 h 6 14
ꢀ12 6 k 6 12
ꢀ32 6 l 6 33
14710
ꢀ10 6 h 6 9
ꢀ34 6 k 6 27
ꢀ16 6 l 6 18
11879
ꢀ10 6 h 6 10
ꢀ12 6 k 6 12
ꢀ17 6 l 6 17
10565
ꢀ30 6 h 6 31
ꢀ10 6 k 6 5
ꢀ25 6 l 6 24
25386
ꢀ15 6 h 6 18
ꢀ19 6 k 6 19
ꢀ24 6 l 6 18
28285
ꢀ13 6 h 6 12
ꢀ23 6 k 6 19
ꢀ23 6 l 6 18
22898
Reflections collected
Unique (Rint
)
4307 (0.0261)
98.7
6707 (0.0193)
99.9
4654 (0.0302)
99.5
8517 (0.0322)
98.1
4471 (0.0461)
100.0
7943 (0.0304)
99.9
Completeness to
2h = 50.5° (%)
Reflections, I P 2
Parameters
r
(I)
3999
165
5930
360
4034
243
6402
326
3689
213
6954
291
R indices (I > 2
r
(I))
R1 = 0.0202,
wR2 = 0.0466
R1 = 0.0230,
wR2 = 0.0474
1.110
R1 = 0.0217,
wR2 = 0.0494
R1 = 0.0284,
wR2 = 0.0514
0.864
R1 = 0.0296,
wR2 = 0.0561
R1 = 0.0398,
wR2 = 0.0584
1.015
R1 = 0.0249,
wR2 = 0.0442
R1 = 0.0492,
wR2 = 0.0478
0.973
R1 = 0.0199,
wR2 = 0.0391
R1 = 0.0293,
R2 = 0.0412
1.016
R1 = 0.0194,
wR2 = 0.0423
R1 = 0.0256,
wR2 = 0.0434
1.037
R indices (all data)
Goodness-of-fit (GOF)
Residual electron
ꢀ1.530/2.437
ꢀ0.392/0.793
ꢀ0.890/2.353
ꢀ0.846/2.729
ꢀ0.624/0.526
ꢀ0.786/0.899
density (minimum/
maximum, e Åꢀ3
)

D.A. Bashirov et al. / Polyhedron 42 (2012) 168–174
173
layered onto it. The two-layer system obtained was placed at ambi-
ent temperature until diffusion of the solvents ceased. Complex 8
was obtained in the form of light-blue crystals suitable for XRD,
0.118 g (ꢁ45%). Found (%): C, 34.2; H, 3.6; N, 3.1. Calculated for
7ꢂ0.5Tol, 8, 9 and 10ꢂ0.5CH2Cl2, respectively. These data can be ob-
tained free of charge via http://www.ccdc.cam.ac.uk/conts/retriev-
ing.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.
C
26H33Cl3Ir2N2OS (%): C, 34.23; H, 3.65; N, 3.07. 1H NMR (d): 7.53
(dd, 1H, het. ligand), 6.84 (d, 1H, het. ligand), 6.50 (d, 1H, het. li-
gand), 1.78 (s, 15H, Cp*), 1.57 (s, 15H, Cp*). 13C NMR (d): 164.69
(s), 158.88 (s), 155.58 (s), 138.60 (s), 110.85 (s), 104.71 (s, C, het.
ligand), 87.12 (s), 86.32 (s, C5(CH3)5), 9.75 (s), 9.43 (s, C5(CH3)5).
Complex 9: A mixture of 0.056 g (0.07 mmol) of 5, 0.010 g
(0.066 mmol) of 3 and 10 mL of toluene was stirred at 80 °C for
24 h. The solution was filtered and the solvent was distilled off.
The residue was dissolved in 6 mL of CH2Cl2 and an equal volume
of hexane was layered onto solution obtained. The two-layer sys-
tem was left at ambient temperature until diffusion of the solvents
ceased. Complex 9 was obtained in the form of red crystals suitable
for XRD, 0.026 g (ꢁ70%). Found (%): C, 34.9; H, 3.7; N, 7.5; S, 5.3.
Calculated for C16H20Cl2IrN3S (%): C, 34.97; H, 3.66; N, 7.64; S,
5.83. 1H NMR (d): 7.42–7.47 (m, 2H, het. ligand), 6.79 (d, 1H, het.
ligand), 4.93 (s, 2H, NH2), 1.53 (s, 15H, Cp*). 13C NMR (d): 155.20
(s), 148.80 (s), 139.07 (s), 133.16 (s), 112.06 (s), 100.65 (s, C, het.
ligand), 86.92 (s, C5(CH3)5), 9.50 (s, C5(CH3)5).
Complex 10: (a) Acenaphtho[1,2-c][1,2,5]thiadiazole (4): At
ꢀ50 °C, a solution of 0.50 g (4.85 mmol) of SCl2 in 20 mL of Et2O
was added to a stirred solution of 1.56 g, (4.81 mmol) of 1,2-bis(tri-
methylsilyl)iminoacenaphthen [35] in 30 mL of Et2O. The reaction
mixture was warmed-up slowly to room temperature, filtered, con-
centrated to a volume of ca. 10 mL, and placed at 5 °C. Compound 4
[36] was obtained in the form of yellow crystals, 0.660 g (ꢁ65%).
Found (%): C, 68.5; H, 2.9; N, 13.2, S, 15.2. Calculated for C12H8N2S
(%): C, 68.55; H, 2.88; N, 13.32, S, 15.25. 1H NMR (d): 7.97 (d, 2H),
7.86 (d, 2H), 7.60 (dd, 2H). 13C NMR (d): 165.91 (s), 141.53 (s),
131.15 (s), 129.35 (s), 128.32 (s), 127.10 (s), 122.54 (s).(b) A mixture
of 0.076 g (0.095 mmol) of 5 and 0.020 g (0.095 mmol) of 4 in 10 mL
of toluene was stirred for 24 h at 80 °C. The solution was filtered,
and the solvent distilled off. The residue was dissolved in 7 mL of
CH2Cl2 and an equal volume of hexane was layered onto solution
obtained. The two-layer system was left at ambient temperature
until diffusion of the solvents ceased. Complex 10 was obtained
with CH2Cl2 solvated in the form of orange crystals suitable for
XRD, 0.036 g (ꢁ60%). Found (%): C, 41.2; H, 3.5; N, 4.1; S, 4.5. Calcu-
lated for C22.5H22Cl3IrN2S (%): C, 41.50; H, 3.40; N, 4.30; S, 4.92. 1H
NMR (d): 8.35 (d, 2H), 8.01 (d, 2H), 7.73 (dd, 2H), 5.27 (s, 0.2H,
CH2Cl2), 1.59 (s, 15H, Cp*). 13C NMR (d): 165.71 (s), 141.44 (s),
131.01 (s), 130.07 (s), 128.35 (s), 126.15 (s), 124.13 (s, C, het. li-
gand), 86.93 (s, C5(CH3)5) 9.45 (s, C5(CH3)5).
Acknowledgments
The authors are grateful to Prof. Dr. Rüdiger Mews for helpful
discussions, and to the Deutsche Forschungsgemeinschaft (project
436 RUS 113/967/0-1 R), the Presidium of the Russian Academy of
Sciences (project 18.17) and the Siberian Branch of the Russian
Academy of Sciences (project 105) for financial support of this
work. N.A.S. thanks the Russian Science Support Foundation for a
2010 Postgraduate Scholarship. We thank Gallyamov Marsel for
the NMR measurements.
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4. Conclusion
It has been found that the reactions of [IrCp*Cl(l -Cl)]2 (5) with
2,1,3-benzothiadiazole (1), its 4-XH (X = O, NH; 2 and 3, respec-
tively) derivatives, and acenapththo[1,2-c][1,2,5]thiadiazole (4) af-
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