Synthesis, structures, and oxidation of iridium(III) alkyl compounds containing thiolate and dithiolate ligands

Article abstract of DOI:10.1002/ejic.200800460

Treatment of [Ir(dtbpy){CH₂CMe₂C^c ₆H₄(Ir-C^c)}(C₆H₄tBu-2)] (1) (dtbpy = 4,4′-di-tert-butyl-2,2′-bipyridyl) with the dichalcogenides R₂Q₂ in refluxing toluene afforded the chalcogenolate-bridged dinuclear complexes [Ir(dtbpy)-{CH₂CMe ₂C⁶₆H₄(Ir-C^c)}] ₂(μ-QR)₂ [RQ = pTolS (2), PhSe (3)]. Similarly, heating a solution of [Rh(dtbpy){CH₂CMe₂-C^c ₆H₄(Ir-C^c)}(CH₂CMe₂Ph)] and p-tolyl sulfide in toluene at reflux gave [Rh(dtbpy){CH₂CMe ₂C^c₆H₄(Ir-C^c)}] ₂(μ-SpTol)₂ (4). Treatment of [Ir(dtbpy)(CH ₂CMe₂Ph)Cl]₂(μ-Cl)₂ with Na(Sxyl) (xyl = 2,6-dimethylphenyl) and Na₂(S∧S) afforded [Ir(dtbpy)(CH₂CMe₂Ph)(Sxyl)₂]₂ (5) and [Ir(dtbpy)-(CH₂CMe₂Ph)(S∧S)]₂ {S∧S₂- = maleonitriledithiolate (6), toluene-3,4-dithiolate (7), benzene-1,2-dithiolate (8)}. Oxidation of compound 8 with AgOTf (OTf- = triflate) resulted in dimerization of the bdt^2- ligand by S-S bond formation and the isolation of [Ir₂(dtbpy)₂(CH ₂Me₂Ph)₂{(bdt)₂}][OTf]₂ (9). The solid-state structures of compounds 2, 3, 4, 7, and 9 were determined. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Full text of DOI:10.1002/ejic.200800460

FULL PAPER
DOI: 10.1002/ejic.200800460
Synthesis, Structures, and Oxidation of Iridium(III) Alkyl Compounds
Containing Thiolate and Dithiolate Ligands
Ka-Wang Chan,[a] Yiu-Keung Sau,[a] Qian-Feng Zhang,[b] Wai-Yeung Wong,[c]
Ian D. Williams,[a] and Wa-Hung Leung*[a]
Keywords: Iridium / S ligands / Oxidation
Treatment of [Ir(dtbpy){CH2CMe2Cc6H4(Ir–Cc)}(C6H4tBu-2)]
(1) (dtbpy = 4,4Ј-di-tert-butyl-2,2Ј-bipyridyl) with the di-
[Ir(dtbpy)(CH2CMe2Ph)(Sxyl)2]2
(5)
and
[Ir(dtbpy)-
∧
∧
(CH2CMe2Ph)(S S)]2 {S S2– = maleonitriledithiolate (6), tolu-
chalcogenides R2Q2 in refluxing toluene afforded the chalco- ene-3,4-dithiolate (7), benzene-1,2-dithiolate (8)}. Oxidation
genolate-bridged
dinuclear
complexes
[Ir(dtbpy)-
of compound 8 with AgOTf (OTf– = triflate) resulted in dimer-
ization of the bdt2– ligand by S–S bond formation and the
isolation of [Ir2(dtbpy)2(CH2Me2Ph)2{(bdt)2}][OTf]2 (9). The
solid-state structures of compounds 2, 3, 4, 7, and 9 were de-
termined.
{CH2CMe2Cc6H4(Ir–Cc)}]2(µ-QR)2 [RQ = pTolS (2), PhSe (3)].
Similarly, heating
a solution of [Rh(dtbpy){CH2CMe2-
Cc6H4(Ir–Cc)}(CH2CMe2Ph)] and p-tolyl sulfide in toluene at
reflux gave [Rh(dtbpy){CH2CMe2Cc6H4(Ir–Cc)}]2(µ-SpTol)2
(4). Treatment of [Ir(dtbpy)(CH2CMe2Ph)Cl]2(µ-Cl)2 with
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2008)
∧
Na(Sxyl) (xyl = 2,6-dimethylphenyl) and Na2(S S) afforded
plexes with thiolate and dithiolate ligands that are known
to stabilize metal ions in unusual oxidation states.[7,8] Of
special interest are metal complexes with benzene-1,2-di-
thiolate (bdt) due to their interesting redox behavior.[8–10]
The electronic structures of oxidized forms of metal–bdt
complexes were studied in detail recently.[10] Although IrIV
species have been generated in solutions by electrochemical
oxidation of IrIII tris(dithiocarbamate) complexes,[11] analo-
gous Ir–bdt complexes have not been isolated. In this paper,
we describe the synthesis and crystal structures of IrIII
dtbpy alkyl complexes containing thiolate and dithiolate li-
gands. It was found that instead of formation of IrIV species
oxidation of the IrIII bdt alkyl complex led to dimerization
of the bdt2– ligand by formation of a S–S bond.
Introduction
Organoiridium compounds containing 2,2Ј-bipyridyl
(bpy) and related ligands are of interest due to the findings
that Ir(bpy) compounds can catalyze selective borylation of
arenes under mild conditions.[1,2] It is believed that Ir(bpy)-
catalyzed borylation involves the oxidative addition of an
IrIII(bpy) boryl species with arene C–H bonds and subse-
quent reductive elimination of boronate esters.[3] Thus, un-
derstanding of organometallic chemistry of higher valent
Ir(bpy) compounds can help develop new Ir catalysts for
C–H activation and functionalization.
Few stable IrIV alkyls and aryls have been isolated,[4,5]
presumably because of the stability of low-spin d6 IrIII com-
pounds, which renders their oxidation difficult. Recently, we
synthesized the irida(III)cycle [Ir(dtbpy){CH2CMe2-
Cc H4(Ir–Cc)}(C6H4tBu-2)] (dtbpy = 4,4Ј-di-tert-butyl-2,2Ј-
6
Results and Discussion
bipyridyl) (1) by alkylation of [Ir(dtbpy)Cl3(dmf)] (dmf =
N,N-dimethylformamide) with PhMe2CCH2MgCl. Com-
pound 1 could be oxidized reversibly to an IrIV species,
which was found to decompose in solutions to give the IrIII
starting material.[6] In an attempt to enhance the stability
of the IrIV state, we sought to synthesize IrIII alkyl com-
Iridacyclic Thiolate Complexes
In an attempt to synthesize high-valent Ir alkyl com-
pounds, the oxidative addition of iridacycle 1 with disul-
fides was studied. Reaction of compound 1 with p-tolyl di-
sulfide in refluxing toluene resulted in a dark material. Col-
umn chromatography on silica led to isolation of the dinu-
[a] Department of Chemistry, The Hong Kong University of Sci-
ence and Technology,
clear thiolate compound [Ir(dtbpy){CH2CMe2Cc H4(Ir–
6
Cc)}]2(µ-SpTol)2 (2) in 45% yield along with unreacted 1
Clear Water Bay, Kowloon, Hong Kong, P. R. China
Fax: +852-2358-1594
(ca. 40%). Similarly, the selenolate-bridged dimer
E-mail: chleung@ust.hk
[Ir(dtbpy){CH2CMe2Cc H4(Ir–Cc)}]2(µ-SePh)2 (3) was syn-
[b] Department of Applied Chemistry, Anhui University of Tech-
nology,
6
thesized from compound 1 and Ph2Se2 (Scheme 1). This
synthetic route can also be used for Rh thiolate alkyl com-
Ma’anshan, Anhui 243002, P. R. China
[c] Department of Chemistry, Hong Kong Baptist University,
Waterloo Road, Kowloon, Hong Kong, P. R. China
pounds. Thus, heating
a
solution of [Rh(dtbpy)-
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W.-H. Leung et al.
FULL PAPER
{CH2CMe2Cc H4(Rh–Cc)}(CH2CMe2Ph)][12] and p-tolyl
6
disulfide in toluene at reflux led to formation of the RhIII
thiolate complex [Rh(dtbpy){CH2CMe2Cc H4(Rh–Cc)}]2-
6
(µ-SpTol)2 (4) (Scheme 2). Heating compound 1 with
Ph2Te2 in toluene at reflux resulted in a brown oil possibly
containing an IrIII tellurolate complex. We have not been
able to purify this brown oily material for further analysis.
Oxidative addition of low-valent metal centers with disul-
fides to give metal bis(thiolate) complexes[13] and C–S re-
ductive elimination from organometallic thiolate com-
plexes[14] is well documented. Thus, it seems reasonable to
assume that the formation of compound 2 involves the oxi-
dative addition of 1 with the S–S bond. Reductive elimi-
nation of 2-tert-butylphenyl p-tolyl sulfide from the IrV
bis(thiolate) intermediate gives the IrIII thiolate product
(Scheme 3). It may be noted that the IrIII thiolate complexes
[Ir(CO)(PPh3)X(SAr)]2(µ-Ar)2 (X = halide, Ar = 4-substi-
tuted 2,6-dinitrophenyl) were synthesized from oxidative
addition of trans-[Ir(CO)X(PPh3)2] with Ar2S2.[15]
Scheme 3. Proposed mechanism for the formation of complexes 2
and 3.
1.90 (d), 0.45 (s) and 0.57 (s) ppm. Consistent with the so-
lid-state structures (see below), the two tert-butyl groups of
the dtbpy ligand in these complexes are magnetically in-
Scheme 1. Reaction of complex 1 with dichalcogenides.
Figure 1. Molecular structure of [Ir(dtbpy){CH2CMe2Cc H4-
6
(Ir–Cc)}]2(µ-SpTol)2 (2). The ellipsoids are drawn at the 30% prob-
ability level.
Scheme 2. Synthesis of complex 4.
Compounds 2–4 are remarkably stable in both the solid
state and CH2Cl2 solutions. They could be purified by col-
1
umn chromatography on silica in air. The H NMR spec-
trum of compound 2 shows two doublets at δ = 1.17 and
1.87 ppm (J = 6.0 Hz) and two singlets at δ = 0.42 and
0.47 ppm, which are assigned to the diastereotopic methyl-
ene (Ha) and methyl (Hb) protons of the iridacycle (see
atom labeling scheme in the Experimental Section), respec-
tively. The corresponding resonances for compound 3 were
found at δ = 1.23 (d), 1.95 (d), 0.48 (s) and 0.56 (s) ppm,
Figure 2. Molecular structure of [Ir(dtbpy){CH2CMe2Cc H4-
6
(Ir–Cc)}]2(µ-SePh)2 (3). The ellipsoids are drawn at the 30% prob-
whereas those for compound 4 occurred at δ = 0.90 (d), ability level.
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Iridium(III) Alkyl Compounds Containing Thiolate and Dithiolate Ligands
equivalent and appear as two singlets in the 1H NMR spec- pound 2, the Ir–S bond opposite the carbon atom
tra.
[2.495(1) Å] is longer than that opposite the nitrogen atom
Compounds 2–4 were characterized by X-ray crystal- [2.345(1) Å] due to the trans influence of the methylene
lography (Figures 1, 2, and 3, respectively). Selected bond group. Similar asymmetric M–Q–MЈ bridges were found in
lengths and angles are summarized in Table 1. The structure compounds 3 [2.575(1) and 2.490(9) Å] and 4 [2.544(7) and
of each of these complexes can be viewed as consisting of 2.344(7) Å]. It may be noted that the Ir–S distances in 2 are
two symmetry-related {M(dtbpy)[CH2CMe2Cc H4(M– shorter than the Ir–Se distances in 3 but comparable to the
6
Cc)](QR)} (M = Ir or Rh, RQ = pTolS or PhSe) fragments Rh–S distances in 4. The Ir–C(phenyl) [2.044(4) and
that are linked together by M–Q–MЈ bridges. Contrary to 2.024(9) Å] and Ir–C(methylene) [2.077(4) and 2.022(9) Å]
compound 1, the phenyl ring of the metallacycle in com- distances of compounds 2 and 3 compare well with those
pounds 2 and 3 is opposite to a pyridyl nitrogen atom, of compound 1 [2.022(4) and 2.073(4) Å, respectively].
whereas the methylene group is trans to a M–Q bond. The The corresponding distances for compound 4 [2.019(3)
same arrangement was found for Rh compound 4. In com- and 2.056(3) Å, respectively] are in good agreement
with those of [Rh(dtbpy){CH2CMe2Cc H4(Rh–Cc)}-
6
(CH2CMe2Ph)].[12] The long M–M separations in these
complexes (3.696, 3.877, and 3.706 Å) indicate the absence
of any direct metal–metal bond.
Ir Neophyl Thiolate and Dithiolate Complexes
Ir(dbpy) neophyl thiolate and dithiolate complexes were
synthesized by reaction of [Ir(dtbpy)(CH2CMe2Ph)Cl]2(µ-
Cl)2 with sodium salts of thiol and dithiol. Thus, treatment
of [Ir(dtbpy)(CH2CMe2Ph)Cl]2(µ-Cl)2 with 2 equivalents of
NaSxyl (xyl = 2,6-dimethylphenyl) afforded the thiolate-
bridged dinuclear compound [Ir(dtbpy)(CH2CMe2Ph)-
(Sxyl)]2(µ-Sxyl)2 (5), whereas that with equimolar amounts
∧
∧
of Na2(S S) gave dimeric [Ir(dtbpy)(CH2CMe2Ph)(S S)]2
2–
{S S = maleonitriledithiolate (mnt2–) (6), toluene-3,4-di-
∧
Figure 3. Molecular structure of [Rh(dtbpy){CH2CMe2Cc H4-
6
thiolate (tdt2–) (7), benzene-1,2-dithiolate (bdt2–) (8)}
(Scheme 4). The 1H NMR spectra for compounds 5–8 show
two singlets due to the tert-butyl protons, indicating that
(Rh–Cc)}]2(µ-SpTol)2 (4). The ellipsoids are drawn at the 30% prob-
ability level.
∧
the two thiolate groups of the S S ligand in each of these
Table 1. Selected bond lengths [Å] and angles [°] for [M(dtbpy)-
complexes are inequivalent. The methylene protons (Ha) in
compound 5 appear as two doublets δ = 1.03 and 1.48 ppm,
whereas those for compounds 6 (δ = 1.52 and 2.48 ppm), 7
(δ = 1.40 and 1.82 ppm), and 8 (δ = 1.38 and 1.84 ppm)
were found at more upfield positions. The methyl protons
of the neophyl ligand for compounds 6–8 appear as singlets
at δ = 1.35, 1.17, and 1.14 ppm, respectively.
Compound 7 was characterized by X-ray crystallography
(Figure 4). Selected bond lengths and angles are listed in
Table 2. The structure consists of two symmetry-related
{Ir(dtbpy)(CH2CMe2Ph)(tdt)} fragments that are linked to-
gether by two Ir–S–IrЈ bridges. Such a thiolate-bridged di-
meric structure is well known for metal bis(dithiolene) com-
pounds.[16] The tdt2– ligand is opposite the dtbpy ligand,
whereas the neophyl ligand is trans to the bridged Ir–S
bond. A similar arrangement is expected for 6 and 8 given
their similar NMR spectral patterns. The two Ir–S(trans to
N) distances [2.324(2) and 2.343(2) Å] in 7 are similar to
those in [Ir2(tdt)3(CO)2(PPh3)2][17] but shorter than the Ir–
S(trans to C) distance [2.491(2) Å] presumably due to the
trans influence of the neophyl group. The Ir–C distance of
2.088(8) Å compares well with that in [Ir(dtbpy)-
(CH2CMe2Ph)Cl]2(µ-Cl)2 [2.132(5) Å].[6]
{CH2CMe2Cc H4(M–Cc)}]2(µ-QR)2.
6
M = Ir,
M = Ir,
M = Rh,
RQ = pTolS (2) RQ = PhSe (3) RQ = pTolS (4)
M–N(trans to phenyl)
M–NЈ(trans to Q)
M–C(phenyl)
M–C(methylene)
M–Q
2.046(3)
2.108(4)
2.044(4)
2.077(4)
2.495(1)
2.345(1)
3.696
2.054(5)
2.109(6)
2.024(9)
2.029(9)
2.575(1)
2.490(9)
3.877
2.057(2)
2.133(2)
2.019(3)
2.542(7)
2.542(7)
2.344(7)
3.706
M–QЈ
M–MЈ
C(phenyl)–M–NЈ
C(phenyl)–M–C(methylene) 81.5(2)
96.2(2)
94.7(3)
82.1(4)
94.7(3)
166.8(3)
76.9(2)
88.4(3)
96.8(2)
166.5(2)
93.9(2)
93.0(2)
93.9(3)
92.0(2)
172.5(2)
96.5(2)
80.1(3)
96.3(9)
81.7(1)
97.9(1)
165.4(1)
77.7(8)
85.9(1)
96.4(7)
164.1(6)
93.4(9)
92.1(6)
95.9(8)
87.8(6)
174.0(8)
97.2(6)
81.4(2)
NЈ–M–C(methylene)
C(phenyl)–M–N
N–M–NЈ
C(methylene)–M–N
C(phenyl)–M–Q
NЈ–M–Q
C(methylene)–M–Q
N–M–Q
C(phenyl)–M–QЈ
N(2)–M–QЈ
98.7(2)
165.0(2)
77.6(1)
86.0(2)
96.8(1)
163.5(1)
93.3(1)
92.0(1)
94.7(1)
88.3(1)
172.3(1)
98.7(1)
80.5(4)
C(methylene)–M–QЈ
N–M–QЈ
Q–M–QЈ
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W.-H. Leung et al.
FULL PAPER
Oxidation of Complex 8
No observable change was found when compound 6 was
treated with Ag(OTf). In contrast, treatment of compound
8 with Ag(OTf) (2 equiv.) afforded a diamagnetic species
characterized as [Ir2(dtbpy)2(CH2CMe2Ph)2{(bdt)2}][OTf]2
(9) containing the binucleating bis(mercaptophenyl) disul-
1
fide ligand [(bdt)2]2– (Scheme 4) The H NMR spectrum of
compound 9 displays well-resolved signals in the normal
region, indicative of diamagnetic nature of the compound.
Unlike compound 8, only two resonances were found for
the bdt protons in 9. It seems likely that the chemical envi-
ronments of the thiolate groups in the bdt ligands in 9 are
similar, and thus resulting in the accidental degeneracy.
Oxidation-induced dimerization of coordinated benzenedi-
thiolates is well precedented.[18] Liaw and coworkers synthe-
sized [Mn2(CO)6{(bdt)2}] by reaction of [Mn(CO)3(bdt)]
with HBF4 or [Cp2Fe][BF4].[18a] Rosenberg and coworkers
reported that oxidation of [M2(CO)10] (M = Mn or Re) with
triethylamine oxide followed by treatment with 3,4-toluene-
dithiol gave [M2(CO)6{(tdt)2}].[18b] The cyclic voltammog-
ram of 8 in CH2Cl2 solution (working electrode: glassy car-
bon, supporting electrolyte: 0.1  [nBu4N][PF6]) displays a
reversible couple at ca. –0.45 V vs. Cp2Fe+/0, which is tenta-
tively assigned as bdt-based oxidation. Under the same con-
ditions, the metal-centered IrIV–IrIII couple for the irida-
Scheme 4. Syntheses of complexes 5–9.
cycle [Ir(dtbpy){CH2CMe2Cc H4(Ir–Cc)}(C6H4tBu-2)] was
6
observed at a higher potential (0.02 V vs. Cp2Fe+/0).[6] Thus,
it seems reasonable to assume that the AgI oxidation of 8
resulted in a transient IrIII–thiyl radical cation species that
dimerized by formation of an S–S disulfide bond.
The identity of 9 was established by X-ray diffraction
analysis. Figure 5 shows the structure of the dication
[Ir2(dtbpy)2(CH2CMe2Ph)2{(bdt)2}]2+
;
selected
bond
lengths and angles are listed in Table 3. The structure of
the dication can be viewed as consisting of two
{Ir(dtbpy)(CH2CMe2Ph)(bdt)}+ fragments linked together
by two Ir–S–IrЈ bridges and an S–S bond. The geometry
around each Ir is roughly octahedral with the neophyl
group opposite the bridged thiolate group. The S–S distance
of the [(bdt)2]2– ligand in 9 [2.317(4) Å] is longer than those
in [Mn2(CO)6{(bdt)2}][2.222(1) Å],[18a] [Mn2(CO)6{(tdt)2}]
[2.2235(8) Å], and [Re2(CO)6{(tdt)2}] [2.235(2) Å],[18b]
probably because of steric effects. Unlike complex 8, in
which the two bdt–Ir chelate rings are placed side by side,
the chelate rings in 9 are rather superimposed, resulting in
a distorted Ir2S4 trigonal prism. As pointed out by one ref-
eree of this paper, the bonding in 9 can also be described
in terms of π*–π* interaction of the two IrS2 moieties in
view of the rather long disulfide S–S distance and the in-
creased separation between both Ir(bdt) chelate rings. The
Ir1–Ir2 separation in compound 9 (3.415 Å) is shorter than
that in compound 7 (3.548 Å) presumably due to the forma-
tion of the S–S bond and/or cationic charge of the complex.
Ir–S(IrЈ) distances [2.341(3) and 2.333(4) Å] are longer than
the Ir–S(disulfide) distances [2.271(3) and 2.259(3) Å]. A
similar result was found for analogous Mn complexes.[18]
The IrЈ–S(trans to C) distances [2.515(3) and 2.509(3) Å]
are similar to that in 7.
Figure 4. Molecular structure of [Ir(dtbpy)(CH2CMe2Ph)(tdt)]2 (7).
The ellipsoids are drawn at the 30% probability level.
Table 2. Selected bond lengths [Å] and angles [°] for
[Ir(dtbpy)(CH2CMe2Ph)(tdt)]2 (7).[a]
Ir1–N1
2.023(7)
2.088(8)
2.343(2)
3.548
Ir1–N12
Ir1–S1#1
Ir1–S1
2.045(7)
2.324(2)
2.491(2)
Ir1–C21
Ir1–S2#1
Ir1–Ir1#1
N1–Ir1–N12
N12–Ir1–C21
N12–Ir1–S1#1
N1–Ir1–S2#1
C21–Ir1–S2#1
N1–Ir1–S1
78.5(3)
88.5(3)
99.3(2)
95.9(2)
90.1(3)
86.5(2)
171.7(2)
87.6(8)
N1–Ir1–C21
N1–Ir1–S1#1
C21–Ir1–S1#1
N12–Ir1–S2#1
S1#1-Ir1–S2#1
N12–Ir1–S1
101.6(3)
171.1(2)
86.8(3)
173.8(2)
86.7(8)
94.6(2)
85.1(7)
C21–Ir1–S1
S2#1-Ir1–S1
S1#1-Ir1–S1
[a] Symmetry operator: #1: –x + 1, –y + 1, –z + 1.
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Iridium(III) Alkyl Compounds Containing Thiolate and Dithiolate Ligands
at 300 MHz. 1H chemical shifts are reported in ppm relative to
SiMe4 (δ = 0 ppm) and were referenced to the proton solvent resi-
due. Infrared spectra were recorded with a Perkin–Elmer 16 PC
FTIR spectrophotometer, and mass spectra were recorded with a
Finnigan TSQ 7000 spectrometer. Elemental analyses were per-
formed by Medac Ltd., Surrey, UK. The compounds
[Ir(dtbpy){CH2CMe2Cc H4(Ir–Cc)}(C6H4tBu-2)] (1), [Ir(dtbpy)-
6
(CH2CMe2Ph)Cl]2(µ-Cl)2,[6] and [Rh(dtbpy){CH2CMe2Cc H4(Rh–
6
Cc)}(CH2CMe2Ph)][12] were prepared as described elsewhere. The
ligand Na2mnt [mnt2– = maleonitriledithiolate] was prepared ac-
cording to a literature method.[19] Hydrogen atom labeling schemes
for the dtbpy and neophyl ligands are shown below.
Figure 5. Molecular structure of the complex dication in 9. The
ellipsoids are drawn at the 20% probability level.
[Ir(dtbpy){CH2CMe2Cc H4(Ir–Cc)}]2(µ-QR)2 [RQ
= pTolS (2),
Table 3. Selected bond lengths (Å) and angles [°] for [Ir2(dtbpy)2-
(CH2CMe2Ph)2{(bdt)2}][OTf]2 (9).
6
PhSe (3]}: To a solution of compound 1 (100 mg, 0.138 mmol) in
toluene (25 mL) was added R2Q2 (0.069 mmol), and the mixture
was heated under reflux overnight. The volatiles were removed in
vacuo, and the residue was purified by silica gel column chromatog-
raphy (Et2O/hexane, 7:3). Recrystallization from CH2Cl2/hexane
gave green crystals suitable for X-ray diffraction analysis.
Ir1–N2
Ir2–N3
Ir1–C28
Ir1–S1
Ir1–S3
Ir2–S3
S1–S4
2.043(10)
2.073(10)
2.137(12)
2.271(3)
2.509(3)
2.333(4)
2.317(4)
Ir1–N1
Ir2–N4
Ir2–C41
Ir1–S2
Ir2–S4
Ir2–S2
Ir1–Ir2
2.051(10)
2.061(12)
2.146(14)
2.341(3)
2.259(3)
2.515(3)
3.415
2: Yield: 45 mg, 45%. 1H NMR (300 MHz, CDCl3, 298 K): δ =
0.42 (s, 6 H, Hb), 0.47 (s, 6 H, Hb), 1.24 (s, 18 H, tBu), 1.48 (s, 18
H, tBu), 1.17 (d, J = 6.0 Hz, 2 H, Ha), 1.87 (d, J = 6.0 Hz, 2 H,
Ha), 2.03 (s, 6 H, Me of pTol), 5.56 (d, J = 8.1 Hz, 4 H, Hortho of
pTol), 5.85 (d, J = 8.1 Hz, 4 H, Hmeta of pTol), 6.47 (dd, J = 7.2
and 1.2 Hz, 2 H, Hortho), 6.84–6.87 (m, 4 H, Hmeta), 6.96 (t, J =
6.9 Hz, 2 H, Hpara), 7.05 (d, J = 1.8 Hz, 2 H, H3), 7.38 (d, J =
1.8 Hz, 2 H, H3), 7.67 (dd, J = 5.7 and 1.8 Hz, 2 H, H2), 8.57 (d,
J = 6.3 Hz, 2 H, H1), 8.96 (dd, J = 5.7 and 1.8 Hz, 2 H, H2), 10.34
(d, J = 6.3 Hz, 2 H, H1) ppm. MS (FAB): m/z = 715.2 [M/2 + 1]+.
C70H86Ir2N4S2·CH2Cl2·H2O (1534.97): calcd. C 55.56, H 5.91, N
3.65; found C 55.64, H 5.88, N 3.67.
N1–Ir1–N2
N1–Ir1–C28
N1–Ir1–S1
N2–Ir1–S2
C28–Ir1–S2
N2–Ir1–S3
C28–Ir1–S3
S2–Ir1–S3
N4–Ir2–N3
N3–Ir2–C41
N3–Ir2–S4
N4–Ir2–S3
C41–Ir2–S3
N4–Ir2–S2
C41–Ir2–S2
S3–Ir2–S2
77.9(4)
89.7(5)
177.4(3)
172.9(3)
87.1(4)
N2–Ir1–C28
N2–Ir1–S1
C28–Ir1–S1
N1–Ir1–S2
S1–Ir1–S2
N1–Ir1–S3
S1–Ir1–S3
99.1(5)
99.7(3)
91.7(4)
98.9(3)
83.46(12)
82.9(3)
96.04(11)
88.0(3)
168.5(3)
85.36(11)
77.9(4)
N4–Ir2–C41
N4–Ir2–S4
C41–Ir2–S4
N3–Ir2–S3
S4–Ir2–S3
N3–Ir2–S2
S4–Ir2–S2
100.6(5)
99.0(3)
92.1(4)
99.3(3)
83.90(12)
83.5(3)
88.2(5)
176.8(3)
172.3(3)
86.4(4)
87.2(3)
167.2(4)
85.40(11)
3: Yield: 32 mg, 30%. 1H NMR (300 MHz, CDCl3, 298 K): δ =
0.48 (s, 6 H, Hb), 0.57 (s, 6 H, Hb), 1.46 (s, 18 H, tBu), 1.62 (s, 18
H, tBu), 1.94 (d, J = 9.9 Hz, 2 H, Ha), 3.14 (d, J = 9.9 Hz, 2 H,
Hortho of PhSe), 5.60 (d, J = 7.2 Hz, 4 H, Hmeta of PhSe), 5.85 (t,
J = 7.2 Hz, 6 H, Hpara of PhSe), 6.47 (dd, J = 6.0 and 2.0 Hz, 2 H,
Hortho), 6.81–6.84 (m, 4 H, Hmeta), 6.92 (t, J = 6.9 Hz, 2 H, Hpara),
7.15 (d, J = 2 Hz, 2 H, H3), 7.30 (d, J = 2 Hz, 2 H, H3), 7.99 (dd,
J = 5.7 and 2.0 Hz, 2 H, H2), 8.71 (d, J = 6.0 Hz, 2 H, H1), 9.52
96.70(11)
Conclusions
We synthesized IrIII alkyl thiolate/dithiolate compounds (dd, J = 5.7 and 2.0 Hz, 2 H, H2), 10.20 (d, J = 6.0 Hz, 2 H, H1)
by (a) reaction of iridacycle 1 with p-tolyl disulfide and (b)
chloride substitution of [Ir(dtbpy)(CH2CMe2Ph)Cl]2(µ-Cl)2
ppm. MS (FAB): m/z = 750.2 [M/2 + 1]+. C68H82Ir2N4Se2·0.5C6H14
(1540.85): calcd. C 55.34, H 5.82, N 3.64; found C 55.29, H 5.77,
N 3.34.
with sodium thiolate/dithiolate. X-ray crystallography con-
firmed that oxidation of IrIII bdt complex 8 with silver tri- [Rh(dtbpy){CH2CMe2Cc H4(Rh–Cc)}]2(µ-SpTol)2 (4): To a solution
6
of [Rh(dtbpy){CH2CMe2Cc H4(Rh–Cc)}(CH2CMe2Ph)] (100 mg,
flate resulted in oxidation of the bdt2– ligand that under-
6
0.157 mmol) in toluene (25 mL) was added p-tolyl disulfide (20 mg,
0.081 mmol), and the mixture was heated at reflux overnight. The
volatiles were removed in vacuo, and the residue was purified by
silica gel column chromatography (Et2O/hexane, 7:3). Recrystalli-
zation from CH2Cl2/hexane afforded orange crystals suitable for X-
went dimerization by formation of an S–S bond.
Experimental Section
1
General Remarks: All manipulations were performed under an at-
mosphere of nitrogen by standard Schlenk techniques. Solvents
were purified, distilled and degassed prior to use. 1H NMR spectra
were measured with a Varian Mercury 300 spectrometer operating
ray diffraction analysis (yield: 55 mg, 56%). H NMR (300 MHz,
CDCl3, 298 K): δ = 0.42 (s, 6 H, Hb), 0.47 (s, 6 H, Hb), 1.24 (s, 18
H, tBu), 1.48 (s, 18 H, tBu), 1.20 (d, J = 6.0 Hz, 2 H, Ha), 1.93 (d,
J = 6.0 Hz, 2 H, Ha), 2.03 (s, 6 H, Me of pTol), 5.53 (d, J = 7.8 Hz,
Eur. J. Inorg. Chem. 2008, 4353–4359
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
4357

W.-H. Leung et al.
FULL PAPER
4 H, pTol), 5.83 (d, J = 8.1 Hz, 4 H, pTol), 6.48 (dd, J = 7.5 and
1.2 Hz, 2 H, Hortho), 6.86 (t, J = 6.0 Hz, 2 H, Hmeta), 6.94 (dd, J =
6.0 and 1.8 Hz, 2 H, HmetaЈ), 6.98 (t, J = 7.5 Hz, 2 H, Hpara), 7.06
(d, J = 1.8 Hz, 2 H, H3), 7.41 (d, J = 1.8 Hz, 2 H, H3), 7.68 (dd, J
= 7.2 and 1.8 Hz, 2 H, H2), 8.37 (d, J = 5.7 Hz, 2 H, H1), 9.02 (dd,
J = 7.2 and 1.8 Hz, 2 H, H2), 10.20 (d, J = 5.7 Hz, 2 H, H1) ppm.
32 mg, 61% with respect to Ir). 1H NMR (300 MHz, CDCl3,
298 K): δ = 1.04 (s, 6 H, Hb), 1.35 (s, 6 H, Hb), 1.45 (s, 18 H, tBu),
1.46 (s, 18 H, tBu), 1.52 (d, J = 10.1 Hz, 2 H, Ha), 2.48 (d, J =
10.1 Hz, 2 H, Ha), 6.19 (d, J = 8.1 Hz, 4 H, Hortho), 6.47 (t, J =
7.5 Hz, 4 H, Hmeta), 6.72 (t, J = 7.2 Hz, 2 H, Hpara), 7.47 (d, J =
5.4 Hz, 2 H, H2), 7.54 (d, J = 1.8 Hz, 2 H, H3), 9.05 (d, J = 5.4 Hz,
MS (FAB): m/z = 622.2 [M/2 + 1]+. C70H86N4Rh2S2·CH2Cl2 2 H, H1) ppm. MS (FAB): m/z = 734.7 [M/2 + 1]+. IR (KBr): ν =
˜
(1338.33): calcd. C 63.72, H 6.63, N 4.19; found C 64.15, H 7.15,
N 3.99.
2188 [ν(CN)] cm–1. C64H74Ir2N8S4 (1468.02): calcd. C 52.36, H
5.08, N 7.63; found C 52.35, H 5.39, N 7.86.
[Ir(dtbpy)(CH2CMe2Ph)(Sxyl)2]2 (5): To a suspension of NaH
(60% in mineral oil, 3 mg, 0.080 mmol) in tetrahydrofuran (10 mL)
at 0 °C was added 2,6-dimethylbenzenethiol (10 mg, 0.072 mmol),
[Ir(dtbpy)(CH2CMe2Ph)(tdt)]2 (7): To a suspension of NaH (60%
in mineral oil, 3 mg, 0.080 mmol) in thf (10 mL) at 0 °C was added
3,4-toluenedthiol (0.037 mmol) over 1 h, and the mixture was
and the mixture was slowly warmed to room temperature and slowly warmed to room temperature and stirred for 2 h. The mix-
stirred for 2 h. The mixture was cooled to 0 °C and [Ir(dtbpy)- ture was cooled to 0 °C and [Ir(dtbpy)(CH2CMe2Ph)Cl]2(µ-Cl)2
(CH2CMe2Ph)Cl]2(µ-Cl)2 (50 mg, 0.036 mmol) was added. After (50mg, 0.036mmol) was added. After stirring at room temperature
stirring at room temperature overnight, the volatiles were removed
in vacuo, and the residue was washed with hexane. Recrystalli-
zation from Et2O at 0 °C afforded a green powder (yield: 35 mg,
overnight, the volatiles were removed in vacuo, and the residue was
washed with hexane. Recrystallization from CH2Cl2/hexane af-
forded dark-yellow crystals suitable for X-ray diffraction (yield:
48 mg, 89% with respect to Ir). 1H NMR (300 MHz, CDCl3,
298 K): δ = 0.65 (s, 6 H, Hb), 1.17 (s, 6 H, Hb), 1.40 (d, J = 10.8 Hz,
1
56% with respect to Ir). H NMR (300 MHz, CDCl3, 298 K): δ =
1.03 (d, J = 16.2 Hz, 2 H, Ha), 1.28 (s, 18 H, tBu), 1.35 (s, 18 H,
tBu), 1.41 (s, 12 H, Hb), 1.48 (d, J = 16.2 Hz, 2 H, Ha), 2.25 (s, 6 2 H, Ha), 1.43 (s, 18 H, tBu), 1.45 (s, 18 H, tBu), 1.82 (d, J =
H, Me of xyl), 2.27 (s, 6 H, Me of xyl), 2.33 (s, 6 H, Me of xyl),
2.38 (s, 6 H, Me of xyl), 5.53 (d, J = 7.2 Hz, 4 H, xyl), 5.76 (t, J =
6.9 Hz, 2 H, xyl), 6.34 (d, J = 7.5 Hz, 4 H, Hortho), 6.54 (t, J =
10.8 Hz, 2 H, Ha), 2.66 (s, 6 H, Me of tdt), 5.16 (s, 2 H, tdt), 5.84
(d, J = 7.2 Hz, 2 H, tdt), 6.10 (d, J = 7.5 Hz, 4 H, Hortho), 6.25 (t,
J = 7.5 Hz, 4 H, Hmeta), 6.34 (t, J = 7.2 Hz, 2 H, Hpara), 6.48 (d, J
6.9 Hz, 4 H, Hmeta), 6.67 (t, J = 7.2 Hz, 2 H, Hpara), 6.78 (t, J = = 7.5 Hz, 2 H, tdt), 6.78 (d, J = 2.4 Hz, 2 H, H3), 7.14 (d, J =
6.9 Hz, 2 H, xyl), 6.89 (d, J = 7.2 Hz, 4 H, xyl), 6.92 (d, J = 2.2 Hz,
2 H, H3), 7.11 (d, J = 2.2 Hz, 2 H, H3), 7.21 (dd, J = 7.2 and
1.8 Hz, 2 H, H2), 7.27 (dd, J = 7.2 and 1.8 Hz, 2 H, H2), 9.01 (d,
J = 6.8 Hz, 2 H, H1), 9.68 (d, J = 6.8 Hz, 2 H, H1) ppm. MS (FAB):
m/z = 731.3 [M/2 – Sxyl]+. C88H110Ir2N4S4·2CHCl3 (1971.26):
calcd. C 54.84, H 5.52, N 2.84; found C 54.91, H 5.57, N 2.83.
2.4 Hz, 2 H, H3), 7.20 (dd, J = 6.3 and 1.8 Hz, 2 H, H2), 7.26 (dd,
J = 6.3 and 1.8 Hz, 2 H, H2), 9.04 (d, J = 6.0 Hz, 2 H, H1), 9.68
(d, J = 6.0 Hz, 2 H, H1) ppm. MS (FAB): m/z = 748.5 [M/2 + 1]+.
C70H86Ir2N4S4·CH2Cl2 (1581.09): calcd. C 53.94, H 5.61, N 3.54;
found C 53.85, H 5.80, N 3.76.
[Ir(dtbpy)(CH2CMe2Ph)(bdt)]2 (8): This compound was prepared
similarly as for compound 7 by using 1,2-benzenedithiol in place of
3,4-toluenedithiol (yield: 36 mg, 60% with respect to Ir). 1H NMR
[Ir(dtbpy)(CH2CMe2Ph)(mnt)]2 (6): To a solution of [Ir(dtbpy)-
(CH2CMe2Ph)Cl]2(µ-Cl)2 (50 mg, 0.036 mmol) in CH2Cl2 (20 mL)
was added Na2(mnt) (15 mg, 0.081 mmol), and the mixture was (300 MHz, CDCl3, 298 K): δ = 0.63 (s, 6 H, Hb), 1.14 (s, 6 H, Hb),
stirred at room temperature overnight. The volatiles were removed
in vacuo, and the residue was washed with hexane and Et2O.
Recrystallization from CH2Cl2/hexane gave a red powder (yield:
1.38 (d, J = 11.1 Hz, 2 H, Ha), 1.43 (s, 18 H, tBu), 1.45 (s, 18 H,
tBu), 1.84 (d, J = 11.1 Hz, 2 H, Ha), 5.28 (d, J = 7.5 Hz, 2 H, bdt),
5.99 (t, J = 6.9 Hz, 2 H, bdt), 6.16 (d, J = 7.5 Hz, 4 H, Hortho),
Table 4. Crystallographic data for complexes 2–4, 7, and 9.
2
3
4
7
9
Formula
Molecular weight
Crystal system
Space group
C70H86Ir2N4S2
1431.95
monoclinic
P21/c
C68H82Ir2N4Se2
1497.70
monoclinic
P21/n
C70H86N4Rh S2
1253.37
monoclinic
P21/c
C70H86Ir2N4S4
1496.07
monoclinic
P21/n
C70H82F6Ir2N4O6S6
1766.16
monoclinic
P21/n
a [Å]
b [Å]
c [Å]
α [°]
12.9414(18)
19.004(3)
13.5637(18)
90
11.439(2)
14.471(3)
18.817(4)
90
12.8896(8)
19.0136(12)
13.6123(9)
90
9.8899(9)
12.4739(12)
26.240(3)
90
16.4417(14)
24.827(2)
20.6900(17)
90
β [°]
112.984(2)
90
3071.0(7)
2
1.549
100(2)
93.912(4)
90
3107.6(11)
2
1.601
100(2)
113.023(1)
90
3070.3(3)
2
1.356
100(2)
99.343(2)
90
3194.1(5)
2
1.556
100(2)
102.751(2)
90
8237.4(12)
4
1.424
293(2)
γ [°]
V [Å3]
Z
ρcalcd. [gcm–3]
T [K]
µ [mm–1]
4.442
5.492
0.650
4.337
3.439
F(000)
1440
16456
6013
0.0504
0.0316, 0.0670
0.0482, 0.0715
0.998
1480
16428
6017
0.0765
0.0492, 0.0687
0.1272, 0.0773
0.995
1312
16362
5970
0.0269
0.0378, 0.0860
0.0432, 0.0882
1.098
1504
15514
5585
0.0715
0.0467, 0.0888
0.0918, 0.0983
1.003
No. of reflections
No. of indep. reflections
Rint
14418
7074
R1[a], wR2 [IϾ2σ(I)]
0.0609, 0.1994
0.1503, 0.1479
[b]
R1, wR2 (all data)
Goodness of fit
[a] R1 = (Σ||Fo| – |Fc||)/(Σ|Fo|). [b] wR2 = [Σw(Fo – Fc ) /Σw(Fo2)2]1/2
.
2
2 2
4358
www.eurjic.org
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2008, 4353–4359

Iridium(III) Alkyl Compounds Containing Thiolate and Dithiolate Ligands
[3] a) D. Kunz, J. F. Hartwig, C. E. Webster, Y. B. Fan, M. B. Hall,
6.28–6.35 (m, 6 H, Hmeta and Hpara), 6.53 (t, J = 7.5 Hz, 2 H, bdt),
6.69 (d, J = 8.1 Hz, 2 H, bdt), 6.76 (d, J = 2.4 Hz, 2 H, H3), 7.09
(d, J = 2.4 Hz, 2 H, H3), 7.15 (dd, J = 6.3 and 1.8 Hz, 2 H, H2),
7.22 (dd, J = 6.3 and 1.8 Hz, 2 H, H2), 9.06 (d, J = 6.0 Hz, 2 H,
H1), 9.72 (d, J = 6.0 Hz, 2 H, H1) ppm. C68H82Ir2N4S4·0.5CH2Cl2
(1510.57): calcd. C 54.47, H 5.54, N 3.71; found C 54.31, H 5.53,
N 3.96.
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[Ir2(dtbpy)2(CH2CMe2Ph)2{(bdt)2}][OTf]2 (9): To a solution of 8
(51 mg, 0.034 mol) in CH2Cl2 was added silver triflate (18 mg,
0.068 mmol, 2 equiv.), and the mixture was stirred at room tem-
perature for 2 h. Recrystallization from CH2Cl2/hexane afforded
brown crystals (yield: 36 mg, 60%) that were suitable for X-ray
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1
diffraction. H NMR (300 MHz, CDCl3, 298 K): δ = 0.50 (s, 6 H,
Hb), 0.76 (s, 6 H, Hb), 0.96 (d, J = 11.6 Hz, 2 H, Ha), 1.44 (s, 18
H, tBu), 1.62 (s, 18 H, tBu), 2.15 (d, J = 11.6 Hz, 2 H, Ha), 5.99
(d, J = 7.9 Hz, 4 H, bdt), 6.44 (d, J = 7.4 Hz, 4 H, bdt), 6.72 (d, J
= 7.5 Hz, 2 H, Hortho), 6.81 (d, J = 7.5 Hz, 2 H, Hortho), 6.88 (d, J
= 6.1 Hz, 2 H, H2), 7.08 (t, J = 7.5 Hz, 2 H, Hpara), 7.51–7.56 (m,
4 H, Hmeta), 7.75 (s, 2 H, H3), 7.92 (d, J = 6.1 Hz, 2 H, H2), 7.98
(s, 2 H, H3), 8.70 (d, J = 7.7 Hz, 2 H, H1), 8.80 (d, J = 5.9 Hz, 2
H, H1) ppm. C70H82F6Ir2N4O6S6·CH2Cl2 (1851.17): calcd. C 46.07,
H 4.57, N 3.03; found C 46.43, H 4.72, N 3.02.
X-ray Crystallography: Crystallographic data and structure refine-
ment parameters for compounds 2–4, 7, and 9 are summarized in
Table 4. Intensity data were collected with a Bruker SMART
APEX 1000 CCD diffractometer by using graphite-monochro-
mated Mo-Kα radiation (λ = 0.71073 Å). The data was corrected
for absorption by using the program SADABS.[20] The structures
were solved by direct methods and refined by full-matrix least-
squares on F2 by using the SHELXTL software package.[21] In
compound 3, the tert-butyl groups of the dtbpy ligand were found
to be disordered. The C12 carbon atom is split into two sites with
0.6 and 0.4 occupancies, whereas C13, C16, and C18 are split into
two sites with 50% occupancy each. In compound 9, the disordered
triflate anions were refined isotropically. Selected bond lengths and
angles for 2–4, 7, and 9 are listed in Tables 1, 2, and 3, respectively.
CCDC-683524 (for 2), -683525 (for 3), -683526 (for 4), -683527
(for 7), and -683528 (for 9) contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
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52, pp. 55–110.
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[18] a) W.-F. Liaw, C.-K. Hsieh, G.-Y. Lin, G.-H. Lee, Inorg. Chem.
2001, 40, 3468–3475; b) N. Begum, M. I. Hyder, S. E. Kabir,
G. M. G. Hossain, E. Nordlander, D. Rhokhsana, E. Rosen-
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Acknowledgments
We thank Dr. Herman H. Y. Sung for solving the crystal structures.
Financial support from the Hong Kong Research Grants Council
(project no. 601705) is gratefully acknowledged. Q.-F. Z. thanks the
Science and Technological Fund of Anhui Province, P. R. China,
for the Outstanding Youth Award (06046100).
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Manual, Bruker AXS Inc., Madison, Wisconsin, USA, 1997.
Received: May 7, 2008
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Published Online: August 26, 2008
Eur. J. Inorg. Chem. 2008, 4353–4359
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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