π-conjugated trinuclear group-9 metalladithiolenes with a triphenylene backbone

Article abstract of DOI:10.1021/ic400110z

Previously, we synthesized π-conjugated trinuclear metalladithiolene complexes based on benzenehexathiol (J. Chem. Soc., Dalton Trans.1998, 2651; Dalton Trans.2009, 1939; Inorg. Chem.2011, 50, 6856). Here we report trinuclear complexes with a triphenylene backbone. A reaction with triphenylenehexathiol and group 9 metal precursors in the presence of triethylamine gives rise to trinuclear complexes 9-11. The planar structure of 11 is determined using single crystal X-ray diffraction analysis. The ligand-to-metal charge transfer bands of 9-11 move to longer wavelengths compared with those of mononuclear 12-14. Electrochemical measurements disclose that the one-electron and two-electron reduced mixed-valent states are stabilized thermodynamically. UV-vis-NIR spectroscopy for the reduced species of 9 identifies intervalence charge transfer bands for 9^- and 9^2-, substantiating the existence of electronic communication among the three metal nuclei. These observations prove that the triphenylene backbone transmits π-conjugation among the three metalladithiolene units.

Full text of DOI:10.1021/ic400110z

Article
pubs.acs.org/IC
π‑Conjugated Trinuclear Group‑9 Metalladithiolenes with a
Triphenylene Backbone
,†
†
†
†
†
Ryota Sakamoto,* Tetsuya Kambe, Satoru Tsukada, Kenji Takada, Ken Hoshiko,
‡
‡
,†
Yasutaka Kitagawa, Mitsutaka Okumura, and Hiroshi Nishihara*
†
Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
Department of Chemistry, Graduate School of Science, Osaka University, 1-1 Machikaneyama, Toyonaka, Osaka 560-0043, Japan
‡
*
S Supporting Information
ABSTRACT: Previously, we synthesized π-conjugated trinu-
clear metalladithiolene complexes based on benzenehexathiol
(
1
J. Chem. Soc., Dalton Trans. 1998, 2651; Dalton Trans. 2009,
939; Inorg. Chem. 2011, 50, 6856). Here we report trinuclear
complexes with a triphenylene backbone. A reaction with
triphenylenehexathiol and group 9 metal precursors in the
presence of triethylamine gives rise to trinuclear complexes 9−
1
1. The planar structure of 11 is determined using single
crystal X-ray diffraction analysis. The ligand-to-metal charge
transfer bands of 9−11 move to longer wavelengths compared
with those of mononuclear 12−14. Electrochemical measurements disclose that the one-electron and two-electron reduced
mixed-valent states are stabilized thermodynamically. UV−vis−NIR spectroscopy for the reduced species of 9 identifies
−
2−
intervalence charge transfer bands for 9 and 9 , substantiating the existence of electronic communication among the three
metal nuclei. These observations prove that the triphenylene backbone transmits π-conjugation among the three
metalladithiolene units.
INTRODUCTION
■
Multinuclear transition metal complexes have attracted
attention of chemists because they exhibit interesting properties
such as mixed-valent (MV) states, spin frustration, catalytic
1
−3
activity, and unique chemical reactivities.
Some of the
features are attributed to electronic and magnetic interactions
among the metal centers, which occur through bridging entities.
π-Conjugated bridges in particular allow multinuclear metal
complexes to exhibit long-range and strong interactions among
3
c,e
their metal nuclei. Recently, we reported the multinucleation
4,5
of metalladithiolene complexes and cluster complexes:
A
considerable portion of this work involved π-conjugated
trinuclear metalladithiolene complexes composed of benzene-
4
hexathiol (BHT) (Figure 1). Thanks to the quasi-aromaticity
of the metalladithiolene five-membered ring, the phenylene
bridge and three metalladithiolene rings formed a highly planar
tetracyclic framework, featuring high levels of π-conjugation
4
(
1−8, Figure 1a). The π-conjugated framework allowed
Figure 1. (a) π-Conjugated metalladithiolenes: Trinuclear complexes
with phenylene (1−8) and triphenylene (9−11) bridging units, and
mononuclear complexes (12−14). (b) Synthetic scheme for 9−11.
intense electronic communication among the metal centers in
the MV states.
Triphenylene is distinctive among polyaromatic hydro-
carbons (PAHs), as it shows 3-fold symmetry, a vast π6-
We expected that the resultant π-conjugated heptacyclic
framework would allow electronic interactions to be
communicated among the metal nuclei over longer distances
conjugation plane, and strong aromatic resonance stabilization.
These features are beneficial in, for example, highly conductive
discotic liquid crystals made of S-alkylated 2,3,6,7,10,11-
7
triphenylenehexathiol (THT).
This article addresses the synthesis of trinuclear metal-
Received: January 16, 2013
ladithiolene complexes 9−11 with group 9 metals (Figure 1a).
©
XXXX American Chemical Society
A
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Inorganic Chemistry
Article
than in BHT-based trinuclear metalladithiolene complexes. The
synthesis, crystal structure, UV−vis−NIR absorption spectra,
density functional theory (DFT) calculation, electrochemistry,
and electronic communication in the reduced MV states were
investigated. Reports of metal complexes based on a THT
8
platform are rare, and none has yet employed the metal-
ladithiolene motif. We also note that there are reports on9
multinuclear ruthenium complexes having hexaazatriphenylene
10
and hexahydroxytriphenylene ligands. They undergo ligand-
based oxidations and reductions. This is in sharp contrast to
our present research, focusing on the reduction and MV state of
the metal center.
Figure 3. (a) ORTEP drawing of 11 with a thermal ellipsoid set at the
50% probability level. (b) Crystal packing structure of 11 (gray, C;
yellow, S; and pink, Ir). Hydrogen atoms and crystal solvents are
omitted for clarity.
RESULTS AND DISCUSSION
■
Synthesis and Identification. The synthetic procedure for
9
−11 is shown in Figure 1b. The addition of THT to
dichloromethane solutions of [Cp*Co(CO)I ],
2
the Cp* ring and triphenylene core, which forms a tetrameric
assembly (Figure 3b).
UV−vis−NIR Absorption Spectroscopy. Absorption
spectra for 9−11 in dichloromethane are shown in Figure 4a:
[
(Cp*RhCl ) ], and [(Cp*IrCl ) ] (Cp* = pentamethylcyclo-
2 2 2 2
pentadienyl group) in the presence of triethylamine gave rise to
target trinuclear complexes 9−11 (see experimental section for
details). In addition to general characterization measurements,
9
−11 were subjected to X-ray photoelectron spectroscopy
(XPS), which revealed the constitutive elements (Figure 2).
Figure 4. (a) UV−vis−NIR absorption spectra (normalized) and (b)
photos of dichloromethane solutions of THT-bridged trinuclear
complexes 9−11.
The wavelength (λmax) and molar extinction coefficient (εmax
)
at the absorption maxima are summarized in Table 1, along
1
Table 1. λmax and ε max for the LMCT of 3−5 and 9−14
10− ε/M−1 cm−1
4
compound
λmax/nm
9
653
557
464
704
590
499
574
500
418
3.67
2.38
5.60
3.21
3.62
3.61
0.93
0.76
1.06
1
0
Figure 2. X-ray photoelectron spectra of (a) 9, (b) 10, and (c) 11.
11
a
3
a
4
Single Crystal X-ray Structure Analysis. Single crystals
of 11 suitable for X-ray diffraction analysis were obtained via
recrystallization from dichloromethane/hexane at room tem-
a
5
1
2
11
13
perature; the ORTEP drawing and crystal packing are shown
in Figure 3, and the crystallographic parameters are detailed in
Supporting Information, Table S1. We note that this is the first
crystal structure reported for a trinuclear metalladichalcogeno-
lene complex based on a triphenylene backbone. All iridium
ions form five-membered iridadithiolene rings, which are fused
with each another via the central triphenylene core. The bond
lengths relating to the iridadithiolene ring (Ir−S, 2.248 Å; S−C,
1
4
a
From ref 4b.
with those of 3−5, and corresponding mononuclear complexes
12−14 (Figure 1a). 9−11 feature intense absorptions in the
visible and NIR region, which are reflected in the vivid solution
color (Figure 4b). According to knowledge on the mono-
nuclear complexes, these absorptions are assigned to singlet
1
.77 Å; C−C, 1.35 Å) are almost identical to those of BHT-
4b
1
4b
bridged 5 (Ir−S, 2.25 Å; S−C, 1.75 Å; C−C, 1.37 Å). Apart
from the Cp* rings, 11 features a planar heptacycle with a slight
bend. The bend stems from intermolecular packing between
ligand-to-metal charge transfer ( LMCT) transitions. The
1
LMCT band of 11 has a shoulder at around 570 nm, which is
3
presumably derived from the LMCT transition induced by the
B
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Inorganic Chemistry
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1
heavy atom effect of the iridium center. The LMCT bands of
THT-bridged trinuclear 9−11 are red-shifted compared with
those of mononuclear 12−14, but the redshift is less prominent
than that associated with BHT-bridged trinuclear 3−5.
(Figure 5b). The same is true for the LUMO, LUMO+1, and
LUMO+2 of 3 and 9 (Figure 5c,d). Unlike the HOMOs, the
stabilization of the LUMOs in 3 and 9 over the LUMO in 12 is
not significant (Figure 5a).
DFT Calculation. To elucidate the result of UV−vis−NIR
absorption spectroscopy, DFT calculations were conducted.
First, results for cobalt complexes 3, 9, and 12 are discussed
3, 9, and 12 were also subjected to time-dependent DFT
(TDDFT) calculations. The visible and NIR absorption of 12 is
governed by the HOMO-1→LUMO transition (Supporting
Information, Tables S3 and S4). Similarly, those of 9 and 3
comprise the HOMO-1→LUMO and HOMO→LUMO
transitions (Supporting Information, Tables S5−S8). This is
consistent with the previous assignment that the visible-NIR
(
Figure 5 and Supporting Information, Figure S1 and Table
1
4b
band is LMCT. The estimated absorption wavelength is in
the order of 12 < 9 < 3 (Supporting Information, Tables S3−
S8), which is consistent with the order observed experimentally
in UV−vis−NIR spectroscopy (Table 1). The destabilization of
the HOMO and HOMO-1, cobaltadithiolene(π), contributes
1
to the redshift of the LMCT in trinuclear 9 and 3 (Figure 5a).
We also conducted DFT and TD-DFT calculations for THT-
bridged trinuclear Rh and Ir complexes 10 and 11. The result is
summarized briefly in combination with that of Co complex 9.
The metal center does not affect the nature of the frontier
orbitals (Supporting Information, Figure S2 and Table S9). The
main transition in the visible and NIR band is also invariant,
1
LMCT (Supporting Information, Tables S10−S13). The order
of the absorption maximum is in the order of 11 < 10 < 9: this
is attributed to the destabilization of the LUMO, the vacant
metal(d) orbital, in 5d Ir and 4d Rh over 3d Co, which is
demonstrated clearly by means of electrochemistry (vide infra).
Electrochemistry. Figure 6 and Table 2 give details and
results for the electrochemical measurements performed for 9−
Figure 5. (a) Frontier orbital diagrams for 12, 9, and 3, estimated
using DFT calculation. (b) HOMO-1, HOMO, and LUMO for 12. (c)
HOMO-1, HOMO, and LUMO for 9. (d) HOMO-1, HOMO, and
LUMO for 3.
S2). The highest occupied molecular orbital (HOMO) and
HOMO-1 of 12 originate from the cobaltadithiolene(π)
Figure 6. Cyclic voltammograms for (a) 9, (b) 10, and (c) 11,
−1
(Figure 5b). Similarly, the cobaltadithiolene(π) orbitals from
measured at a scan rate of 100 mV s in 0.1 M n-Bu NClO −PhCN
4
4
the three dithiolene units are responsible for the HOMO,
HOMO-1, and HOMO-2 in 3 and 9 (Figure 5c,d, and
Supporting Information, Figure S1). The HOMO and HOMO-
at 298 K, and (d) differential pulse voltammograms for 9−11
measured under the same conditions.
1
levels of 3 and 9 are subject to destabilization compared with
11 in 0.1 M n-Bu NClO −PhCN at room temperature. As a
4
4
the HOMO level of 12, which is caused by π-conjugation
transmitted by the triphenylene and phenylene cores (Figure
reference, the results for 3−5 and 12−14 are reproduced in
Table 2. 9−11 all show reversible reductions. Differential pulse
voltammograms (Figure 6d) and their deconvolution (Support-
ing Information, Figure S3) disclose that the reduction wave is
composed of three one-electron reductions. Judging from the
DFT calculations described above and the previous result on
5
a). The destabilization is more significant in 3 than in 9,
indicative of the distance decay of the π-conjugation. On the
other hand, the lowest unoccupied molecular orbital (LUMO)
of 12 receives a substantial contribution from the vacant Co(d)
C
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Inorganic Chemistry
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Table 2. Formal Potentials (E°′) and Comproportionation
CONCLUSIONS
■
Constants (K ) for the Reduction of 3−5 and 9−14
c
Cyclic trinuclear metalladithiolene complexes of group 9 metals
9−11 are synthesized using THT as a π-bridging ligand. The
single crystal X-ray structure of 11 features a planar π-
conjugated heptacyclic framework. 9−11 possess intense
absorptions in the visible and NIR region, which are assigned
comproportionation
+
potential/V vs Fc /Fc
constant
E ′(X2−/
0
E ′(X /
0
−
E ′(X/
0
log
log
c
3
−
2−
−
Kc(X2−)
−
compd.
X
)
X
)
X )
K (X )
1
1
9
−1.46
−1.76
−2.18
−1.92
−2.18
−2.35
−1.38
−1.70
−2.11
−1.58
−1.93
−2.21
−1.31
−1.64
−2.05
−1.35
−1.74
−2.12
−1.42
−1.74
−2.11
1.4
1.0
1.2
5.8
4.2
2.4
1.2
1.0
1.0
3.9
3.2
1.5
to LMCT transitions. The LMCT bands of 9−11 are red-
shifted compared with those of the corresponding mononuclear
complexes 12−14. 9−11 undergo successive three one-electron
reductions with respect to the metal nuclei. Chemically reduced
1
1
3
4
5
1
1
1
0
1
a
a
a
−
2−
9
and 9 show IVCT bands in the NIR region, which
indicates that the metal nuclei possess electronic communica-
tion. These experimental facts prove that the triphenylene core
transmits π-conjugation among the three metalladithiolene
units.
2
3
4
a
From ref 4b.
EXPERIMENTAL SECTION
■
General Procedures. All reactions were carried out under an
argon or a nitrogen atmosphere. Column chromatography was
performed using Silica Gel 60 N (Kanto Chemicals, spherical, neutral)
4
b
metalladithiolenes with group 9 metals, the series of
reductions is derived from the three metal centers. In addition,
the stepwise reduction of the three equivalent metal centers
1
13
or Aluminum oxide 90 (Merck, basic). H (500 MHz) and C (126
MHz) NMR spectra were recorded on Bruker-DRX500 spectrometer
using CHCl /CDCl (δ 7.25, δC 77.00) or CDHCl /CD Cl (δ
H
−
2−
indicates that the MV species (i.e., X and X ) are stabilized
3
3
H
2
2
2
−
thermodynamically. The comproportionation constants K (X )
and K (X ), are described by eqs 1 and 2
5.32, δ 53.84) as an internal standard. MALDI-TOF-MS and ESI-
C
c
2−
12a
TOF-MS were recorded on Shimadzu/KRATOS AXIMA CFR
spectrometer and Waters LCTPremierXE spectrometer, respectively.
UV−vis−NIR spectra were recorded on JASCO V-570 spectrometer.
XPS was obtained using PHI 5000 VersaProbe (ULVAC-PHI, INC.).
Al Kα (15 kV, 25 W) was used as an X-ray source, and the beam was
c
−
− 2
2−
K (X ) = [X ] /[X][X ]
c
−
−
2−
=
exp[(E°′(X/X ) − E°′(X /X ))F/RT]
(1)
2
focused on a 100-μm area. The spectra were analyzed using MultiPak
2
−
2− 2
−
3−
Software and standardized using a peak of C(1s) emerging at 284.6 eV.
The sample was immobilized on the sample stage using a conductive
adhesive tape. X-ray diffraction data were collected using Rigaku
VariMax with Rigaku Saturn CCD system equipped with a rotating-
anode X-ray generator that emits graphite-monochromated MoKα
radiation (0.7107 Å). Empirical absorption corrections using
equivalent reflections and Lorentzian polarization correction were
performed using Crystal Clear 1.3.6. The structures were solved using
K (X ) = [X ] /[X ][X ]
c
−
2−
2−
3−
=
exp[(E°′(X /X ) − E°′(X /X ))F/RT]
(
2)
n
n
where [X ] is the concentration of chemical species X , and
0
n+1
n
n+1
n
E ′(X /X ) is the formal potential of the X /X redox
couple. The log K values are collected in Table 2. These values
c
2
14
SHELXS-97 and refined against F using SHELXL-97.
suggest that the stabilization of the MV states in 9−11 is
DFT Calculation. DFT and TDDFT calculations were performed
smaller than that in 3−5 because of the distance attenuation
1
5
on Gaussian 09. All optimized structures were obtained at B3LYP
level of theory. As the basis sets, 6-31G* is used for complexes 3, 9,
and 6-31+G* for 12, respectively. For the complexes 10 and 11,
Lanl2TZf and 6-31+G* basis sets are used for the metal ions and
ligands, respectively. Molecular orbitals and excited states were
obtained at the B3LYP/6-31+G* for complexes 3, 9, and 12, and
B3LYP/(Lanl2TZf, 6-31+G*) for 10, 11. The solvent effect
(
intermetal distance: 11.71 Å for 9, and 7.41 Å for 3, from DFT
calculations), but is still appreciable.
Electronic Communication. Electronic communication in
MV states surely has a positive contribution to K , though,
other factors such as a Coulombic contribution make K an
unreliable measure for electronic communication.
reported previously that 3−5 enjoyed electronic communica-
tion among the three metal nuclei in the reduced MV states.
c
c
1
2b−f
We
16
(
dichloromethane) was considered using the PCM method. For
4a,b
the full geometry optimization of the complexes, all symmetry
restrictions are turned off during the computation. The C3v symmetry
Here we also investigate electronic communication in 9 by
means of chemical reduction using a sodium mirror, followed
by UV−vis−NIR spectroscopy. A three-step UV−vis−NIR
of the trinuclear complexes becomes C because Cp* ligands are
1
slightly rotated cooperatively against the symmetry. Owing to the
lower molecular symmetry, the irreducible representations of the
molecular orbitals are not available.
−
2−
3−
spectral change corresponds to 9→9 →9 →9 (Supporting
−
2−
Information, Figure S4). Among these species, MV 9 and 9
show a weak but broad absorption in the NIR region (900−
500 nm). The NIR absorption is assignable to an intervalence
charge transfer (IVCT) band. Unfortunately, we cannot
quantify the off-diagonal matrix coupling element H using
Hush’s equation because the reduction of the LMCT band
overlaps on the IVCT band significantly. We note that a
trinuclear cobalt complex based on benzenehexathiol 1 also
showed disappearance of the LMCT band upon reduction to
, 1 , and 1 . Nevertheless, we can still conclude that 9
Electrochemistry. Cyclic voltammetry and differential pulse
voltammetry were performed on BAS ALS750A analyzer. A glassy
1
carbon disc electrode was used as a working electrode, a platinum wire
+
as a counter electrode, and an Ag /Ag (0.01 M AgClO
in 0.1 M n-
4
Bu NClO /acetonitrile) homemade electrode as a reference electrode.
4
4
ab
1
3
1
Ferrocene was used as an internal standard. The concentration of the
samples was 0.5 mM, and the solution was degassed by Ar bubbling.
Chemical Reduction of 9. A 10 mm × 10 mm quartz
spectrometric cell was equipped with a pyrex glass tube appended
by glass branches. After 9 and Na were placed in one branch and
another branch, respectively, the glassware was connected to a high
vacuum line. A sodium mirror was deposited by depressurization, and
tetrahydrofuran (THF) was transferred to the branch holding 9 by
1
−
2−
3− 4a
1
expresses electronic communication over the long distance,
which is transmitted by the π-conjugated triphenylene core.
D
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Inorganic Chemistry
Article
vacuum distillation. Finally, the glassware was sealed off. Stepwise
reduction of 9 was carried out by contacting the sample solution with
the sodium mirror iteratively. UV−vis−NIR spectroscopy was
conducted by transferring the sample solution to the spectrometric
cell.
10.14 (s), 91.80 (s), 122.97 (s), 125.52 (s), 152.10 (s); Anal. Calcd for
C H Ir S : C, 41.27; H, 3.68. Found: C, 41.62; H, 3.96%; MALDI-
TOF-MS m/z 1397 [M] .
48
51 3 6
+
ASSOCIATED CONTENT
Supporting Information
■
Materials. Dichloromethane was purchased from Asahi Glass Co.
Ltd. Hexane was purchased from Kanto Chemicals. All solvents were
distilled from calcium hydride and dried over molecular sieves 4A.
Lithium (ribbon) was purchased from Sigma-Aldrich Co. Triethyl-
amine was purchased from Kanto Chemicals. Hexamethylthiotriphe-
19,20
*
S
Crystallographic parameters of 11, frontier orbitals and their
energies for 12, 9, and 3, TD-DFT calculation for 12, 9, and 3,
frontier orbitals and their energies for 9−11, TD-DFT
calculation for 10 and 11, deconvolution of the differential
pulse voltammograms of 9−11, UV−vis−NIR spectral change
1
7
18,19
19,20
nylene, Cp*Co(CO)I2,
(Cp*RhCl2)2
and (Cp*IrCl2)2
were prepared according to the methods in the literatures.
Mononuclear complexes 12, 13, and 14 were synthesized
according to previous literatures.
21
22
22
−
2−
3−
of 9 upon reduction to 9 , 9 , and 9 , and cif file for 11. This
material is available free of charge via the Internet at http://
pubs.acs.org.
Synthesis of Triphenylenehexathiol (THT). Li (cut from a Li
ribbon, 0.45 g, 65 mmol) was added to liquid NH (ca. 70 mL) at −78
3
°C. Then hexamethylthiotriphenylene (0.86 g, 1.7 mmol) was added
AUTHOR INFORMATION
Corresponding Author
*E-mail: sakamoto@chem.s.u-tokyo.ac.jp (R.S.), nisihara@
chem.s.u-tokyo.ac.jp (H.N.).
to the suspension, and stirred for 3.5 h at −78 °C. Degassed methanol
12 mL) was added cautiously until the blue color disappeared. The
flask was allowed to warm to room temperature over 1.5 h. Degassed
0% aqueous HCl (ca. 140 mL) was added, so that white solid was
■
(
1
precipitated. The solid was filtrated using a glass filter and washed with
Notes
Et O and dichloromethane. Drying under vacuum gave THT as white
2
The authors declare no competing financial interest.
solid (653 mg, 91%). THT decomposes rapidly under an aerobic
atmosphere. Therefore, it should be handled under an inert
atmosphere. Anal. Calcd for C H S ·0.5H O: C, 50.31; H, 3.05.
ACKNOWLEDGMENTS
1
8
12
6
2
■
+
Found: C, 50.49; H, 3.05%. MALDI-TOF-MS m/z 421 [M+H] . No
H NMR signal was found because of low solubility.
This work was supported by Grants-in-Aid from MEXT of
Japan [Nos. 24750054 and 21108002, area 2107 (Coordination
Programming)], JSPS Research Fellowship for Young Scien-
tists, and the Global COE Program for Chemistry Innovation.
1
Synthesis of [(C (C H S CoCp*) )] (9). To a suspension of THT
6
4
2
2
3
(
42 mg, 0.10 mmol) in dichloromethane (50 mL) was added
triethylamine (0.10 mL, 0.70 mmol). Then Cp*Co(CO)I (0.14 g,
2
0
.30 mmol) was added to the reaction mixture. The resultant
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■
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1
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3
13
1
CD Cl ) δ 1.97 (s, 45H), 8.90 (s, 6H); C{ H} NMR (126 MHz,
2
2
CD Cl ) δ 10.31 (s), 91.42 (s), 123.11 (s), 124.48 (s), 153.71 (s);
2
2
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4
8
51
3
6
6
14
2
2
+
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9
96.0302.
Synthesis of [(C (C H S RhCp*) )] (10). To a suspension of
6
4
2
2
3
THT (21 mg, 0.052 mmol) in dichloromethane (15 mL) was added
triethylamine (52 μL, 0.37 mmol). A dichloromethane solution (10
mL) of (Cp*RhCl ) (47 mg, 0.076 mmol) was added to the reaction
(c) Mu
̈
ller, A.; Jostes, R.; Eltzner, W.; Nie, C.-S.; Diemann, E.;
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Chem. Res. 1997, 30, 383−391.
2
2
mixture. The resultant suspension was stirred for 2 h at room
temperature. Then, the solution was filtered off, and the filtrate was
evaporated in vacuo. The crude product was purified by aluminum
oxide (basic, deactivated with 10w% water) column chromatography
eluted using dichloromethane, and the purple band was collected.
Evaporation of the solvent gave 10 as purple powder (3.1 mg, 5.5%).
(3) (a) Ferrer, S.; Lloret, F.; Bertomeu, I.; Alzuet, G.; Borras
́
, J.;
García-Granda, S.; Liu-Gonzalez, M.; Haasnoot, J. G. Inorg. Chem.
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1
H NMR (500 MHz, CD Cl ) δ 2.07 (s, 45H), 8.97 (s, 6H); Anal.
2
2
Calcd for C H Rh S ·0.2CH Cl ·C H : C, 48.50; H, 4.54. Found:
4
8
51
3
6
2
2
6
14
+
C, 48.28; H 4.76%; MALDI-TOF-MS m/z 1128 [M] ; HR-ESI-TOF-
MS: m/z: Calcd for C H Ir S : 1127.9480 [M] , Found: 1127.9502.
+
48
51 3 6
Synthesis of [(C (C H S IrCp*) )] (11). To a suspension of THT
6
4
2
2
3
(
210 mg, 0.50 mmol) in dichloromethane (500 mL) was added
triethylamine (0.51 mL, 3.6 mmol). A dichloromethane solution (20
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Soc., Dalton Trans. 1998, 2651−2656. (b) Shibata, Y.; Zhu, B.-H.;
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2
2
mixture. The resultant suspension was stirred for 3 h at room
temperature. Then the solution was filtered off, and the filtrate was
evaporated in vacuo. The crude product was purified by silica gel
column chromatography eluted using dichloromethane/hexane (4:1 v/
v), and the second yellow-orange band was collected. Evaporation of
1
the solvent gave 11 as gold powder (423 mg, 61%). H NMR (500
MHz, CDCl ) δ 2.19 (s, 45H), 9.27 (s, 6H); (500 MHz, CD Cl ) δ
3
2
2
13
1
2
.18 (s, 45H), 9.21 (s, 6H); C{ H} NMR (126 MHz, CD Cl ) δ
2 2
E
dx.doi.org/10.1021/ic400110z | Inorg. Chem. XXXX, XXX, XXX−XXX

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dx.doi.org/10.1021/ic400110z | Inorg. Chem. XXXX, XXX, XXX−XXX