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1. INTRODUCTION
N-Heterocyclic carbenes (NHCs) and their transition metal
complexes have been studied extensively over the last decade.1
Due to their electronic and steric properties, NHCs have found
many applications as ligands in coordination chemistry,1,2 as
building blocks for metallosupramolecular complexes,3 as
organocatalysts4 and their transition metal complexes are
used in a broad array of catalytic applications.5 While transition
metal NHC complexes containing one metal center have been
thoroughly studied, there are only a few examples for NHC (or
azolato) ligands acting as a bridging ligands in dinuclear
complexes, where one metal is bound at the carbene (or
azolato) carbon atom and another one is bound at the
unsubstituted ring-nitrogen (A in Figure 1).6 Such structures
are possibly promising candidates as catalysts for unique
transformations through cooperative action of the two metal
centers.7 It has been shown that N-deprotonation of platinum
or palladium complexes bearing protic NH,NR-NHC ligands
leads to homodinuclear complexes (B in Figure 1) with a head-
to-tail (H−T) orientation of the bridging ligands.8 Similar
dinuclear complexes of type B have been obtained from the Figure 1. Selected dinuclear complexes with C,N-bridging azolato
oxidative addition of 2-chloro-N-methylbenzimidazole to ligands.
[Pt(PPh3)4]9 and by treatment of an iron(II)−di-NHC
complex with PhLi (C in Figure 1).10 The formation of after substitution of the two cod ligands for four CO ligands
homodinuclear head-to-head (H−H) complexes has been was H−H complex D characterized by X-ray diffraction.11a
proposed for the reaction of [Ir(cod)(μ-Cl)]2 with lithium N-
benzylimidazolate. However, the cod complexes could not be Received: February 4, 2019
characterized conclusively by NMR spectroscopy and only Published: April 16, 2019
The reaction of the more bulky substituted N-mesityimidazole metalated 1,5,6-trimethylbenzimidazolate ligand in [5] is
with [Ir(cod)(μ-Cl)]2 yielded a mixture of H−H and H−T indicated in the 1H NMR spectrum by the absence of a
complexes.11b Finally, a mononuclear ruthenium(II) complex resonance for H2 proton, which was recorded at δ = 7.70 ppm
bearing a tridentate ligand with two protic pNHC donors can in ligand precursor 1. In addition, the 13C{1H} NMR spectrum
bind a second metal center after deprotonation of the ring-NH of [5] exhibited the typical resonance for the metalated azolato
functions with n-BuLi (E in Figure 1).12 carbon atom at δ = 192.5 featuring a 1JC,Rh coupling constant of
1
We became interested in the preparation of homo- and J = 49.8 Hz, which clearly indicates the presence of a complex
heterodinuclear complexes with μ-C,N bridging NHC ligands with a Rh−Cazolato bond.
and in a detailed NMR spectroscopic characterization of the Distinction between the head-to-head versus the head-to-tail
possible isomeric H−H and H−T isomers. Herein, we report complexes can be made by spin correlation spectroscopy
the preparation of homo- and heterodinuclear complexes of IrI (1H,1H-COSY) as has been suggested for related complexes.11a
and RhI obtained from C2/8-deprotonated N-methylimida- For the head-to-tail complexes, featuring a C2-symmetry axis,
zole, 1,5,6-trimethylbenzimidazole and caffeine and their one spin system is expected with 12 resonances for the two
detailed 1H NMR spectroscopic characterization. chemically equivalent cod ligands. In contrast, the head-to-
head complexes feature a mirror plane (CS) that cuts through
2. RESULTS AND DISCUSSION both of the chemically non-equivalent cod ligands. Thus, two
Two geometrical isomers can be formed if N1-alkylated, azoles spin systems, each comprising six resonances for each 1/2 cod
(imidazoles and benzimidazoles) are deprotonated and used as ligand, are to be expected. The 1H,1H-COSY NMR spectrum
C,N-bridging ligands for the generation of dinuclear of [5] (Figure 2) does exhibit two separate spin systems,
complexes. The bridging ligands could be orientated head-to-
tail (H−T, Figure 1, B,C) or head-to-head (H−H, Figure 1,
D). Reaction of in situ generated lithium N-methylimidazolate
or 1,5,6-trimethylbenzimidazolate with a stoichiometric
amount of [M(cod)(μ-Cl)]2 (M = Rh, Ir) in tetrahydrofuran
(THF) leads exclusively to the air-sensitive homodinuclear H−
H complexes [2]−[5] (Scheme 1). The formation of a mixture
isomer ratio is based on the integrals of the resonances for the 2D NMR spectroscopy and by X-ray diffraction studies with
cod protons in the 1H NMR spectra of the complex mixtures dirhodium complexes [3] and [5]. The reaction of in situ
(see the Supporting Information, Figures S15 and S17). lithiated N-methylbenzimidazolate with an equimolar mixture
Separation of the H−H from the H−T complexes was of [Rh(cod)(μ-Cl)]2 and [Ir(cod)(μ-Cl)]2 led to a mixture
impossible by chromatography and all corresponding attempts composed of the heterodinuclear complex [6] as a major
led to decomposition. reaction product and the two homodinuclear complexes [4]
NMR spectroscopy data revealed two sets of resonances for and [5]. However, a stepwise reaction sequence via the
each complex, which can be assigned to the different isomers lithiated monoiridium complex [7] followed by metalation of
of complexes [8] and [9]. Resonances for the azolato carbon the two ring-nitrogen atoms with [Rh(cod)(μ-Cl)]2 allowed
atoms were recorded in the 13C{1H} NMR spectra at δ = 182.6 the preparation of pure [6] in good yield. The lithiated
ppm ([8H−H]), 178.6 ppm ([8H−T]) and at δ = 188.7 ppm (d, complex [7] constitutes a perfect precursor for the preparation
1
JRhC = 50.0 Hz, [9H−H]), 183.2 (d, 1JRhC = 48.2 Hz, [9H−T] of additional heterodinuclear complexes that might possess
(see the Supporting Information, Figures S16 and S18). unique properties owing to the presence two different metal
Crystals of [9H−T]·C4H8O suitable for an X-ray diffraction centers in close proximity to each other.7,15 In addition,
study were obtained by slow diffusion of n-hexane into a mixtures of homodinuclear head-to-head and head-to-tail
saturated solution of the complex mixture [9H−T]/[9H−H] in complexes [8] and [9] have been synthesized by using caffeine
THF at ambient temperature. The molecular structure is as the η 2 ,μ-C,N-azolato ligand precursor and lithium
depicted in Figure 6. Any intramolecular interaction between diisopropylamide as the base.
the rhodium atoms can be excluded due to long Rh(1)···Rh(2)
separation of 3.1878(2) Å. 4. EXPERIMENTAL SECTION
4.1. General Procedures. All preparations were carried out under
an argon atmosphere using conventional Schlenk techniques or in a
glovebox. Solvents were dried and degassed by standard methods
prior to use. Compound 1-methylimidazole was purchased from Alfa
Aesar, and [Rh(cod)(μ-Cl)]216 and [Ir(cod)(μ-Cl)]217 were prepared
as described in the literature. NMR spectra were recorded on a Bruker
AVANCE I 400 or a Bruker AVANCE III 400 NMR spectrometer.
Chemical shifts (δ) are expressed in ppm downfield from
tetramethylsilane or using the residual protonated solvent signal as
an internal standard. Coupling constants are expressed in Hertz. ESI-
HRMS spectra were obtained with an Orbitrap XL spectrometer.
MALDI spectra were obtained with a Bruker Reflex IV spectrometer.
Assignment of the proton NMR resonances was made via spin
correlation spectroscopy (COSY).
4.2. Synthesis of Compound 1. A sample of 5,6-dimethylbenz-
imidazole (1.90 g, 13.0 mmol) was dissolved in acetonitrile (40 mL).
Figure 6. Molecular structure of complex of [9H−T] in [9H−T]·C4H8O An aqueous solution of NaOH (20 mL, 25 wt %) was added and the
(50% displacement ellipsoids, hydrogen atoms have been omitted for mixture was cooled to 0 °C. Then, a solution of methyliodide (0.80
clarity). Selected bond lengths (Å) and angles (deg): Rh1···Rh2 mL, 13.0 mmol) in acetonitrile (20 mL) was added slowly and the
3.1878(2), Rh1−N21 2.133(2), Rh1−C8 2.021(2), Rh2−N9 reaction mixture was stirred at ambient temperature for 3 d. The
2.134(2), Rh2−C20 2.023(2), N9−C8 1.372(2), N7−C8 1.357(2), solvents were removed in vacuo and the resulting residue was
N19−C20 1.361(2), N21−C20 1.368(3); C8−Rh1−N21 82.95(7), extracted with dichloromethane (3 × 20 mL). The combined organic
N9−Rh2−C20 84.44(7), N7−C8−N9 108.5(2), N19−C20−N21 phases were dried over MgSO4 and the solvent was removed under
108.5(2). reduced pressure to give 1 as a white solid. Yield: 1.34 g (8.4 mmol,
65%). 1H NMR (400 MHz, CDCl3): δ (ppm) 7.70 (s, 1H, H2), 7.54
(s, 1H, H5), 7.12 (s, 1H, H8), 3.73 (s, 3H, H12), 2.38 (s, 3H, H11),
The formation of complex mixtures containing both 2.36 (s, 3H, H10). 13C{1H} NMR (101 MHz, CDCl3): δ (ppm)
geometric isomers ([H−H] and [H−T]) when C8-deproto- 142.7 (C2), 142.3 (C4), 133.0 (C9), 131.9 (C6), 130.7 (C7), 120.1
nated caffeine is used as bridging C,N-ligand must be caused (C5), 109.4 (C8), 30.8 (C12), 20.4 (C11), 20.1 (C10). MS (MALDI-
by the weaker σ-donor properties of the caffeine N9-atom TOF, matrix DCTB) m/z (%): 161 (100) [1 + H]+. Anal. Calcd for
owing to the electron withdrawing backbone compared to the 1: C, 74.96; H, 7.55; N, 17.49. Found: C, 73.91; H, 7.36; N, 17.16.
N3-atom in the bridging azolato ligands in complexes [2]−[5]. 4.3. General Procedure for the Synthesis of Complexes [2]
As a result, a metal atom coordinated by two ring-nitrogen and [3]. A sample of 1,5,6-trimethylbenzimidazole (16.0 mg, 0.10
mmol) was dissolved in THF (5 mL) and cooled to −78 °C before n-
atoms of the caffeine-derived bridging ligand is less stabilized BuLi (0.08 mL, 0.13 mmol of an 1.6 M solution in n-hexane) was
than one coordinated by one ring-nitrogen atom and a carbon added. The reaction mixture was stirred for 2 h at −78 °C. A sample
atom from the second bridging ligand, leading to the formation of complex [Ir(cod)(μ-Cl)]2 or [Rh(cod)(μ-Cl)]2 (0.05 mmol, 33.6
of the H−T isomer next to the H−H isomer. This effect is mg or 24.7 mg, respectively) was added and the solution was stirred
more pronounced for the rhodium complex, thus leading to a for 12 h while it was allowed to warm up to ambient temperature. The
larger ration of 0.7:0.3 (H−T/H−H) compared to the iridium solvent was removed in vacuo and the resulting residue was washed
complex (0.5:0.5). with methanol (2 × 5 mL) and dried under reduced pressure.
4.3.1. Characterization of Complex [2]. Complex [2] was
3. CONCLUSIONS obtained as a red solid. Yield: 18 mg, 0.235 mmol, 47%. 1H NMR
(400 MHz, THF-d8): δ (ppm) 6.88 (d, 3JHH = 1.5 Hz, 1H, H4), 6.78
Four homodinuclear complexes [2]−[5] have been prepared, (d, 3JHH = 1.5 Hz, 1H, H5), 4.22−4.14 (m, 1H, cod-CH), 4.00−3.90
possessing two bridging η2,μ-C,N-azolato ligands. The head-to- (m, 1H, cod-CH), 3.63 (s, 3H, H6), 3.58−3.57 (m, 1H, cod-CH),
head geometry and the different coordination environments of 3.33−3.26 (m, 1H, cod-CH), 2.39−2.25 (m, 4H, cod-CH2), 2.04−
the two metal centers of these complexes were confirmed by 1.97 (m, 2H, cod-CH2), 1.71−1.63 (m, 2H, cod-CH2). 13C{1H}
NMR (101 MHz, THF-d8): δ (ppm) 175.3 (C2), 125.7 (C4), 120.1 a red solid. Yield: 64 mg (of the complex mixture). 1H NMR (400
(C5), 70.8 (cod-CH), 70.4 (cod-CH), 64.8 (cod-CH), 59.6 (cod- MHz, THF-d8, only resonances for the main component [6] are
CH), 35.5 (s, C6), 33.3 (cod-CH2), 33.0 (cod-CH2), 32.7 (cod- listed): δ (ppm) 7.39 (s, 1H, H5), 6.81 (s, 1H, H8), 5.13−5.02 (m,
CH2), 32.6 (cod-CH2). HRMS (ESI, positive ions) m/z: 763.2086 1H, cod-CH), 4.46−4.40 (m, 1H, cod-CH), 4.02−3.92 (m, 2H, cod-
[[2] + H]+ (calcd for [[2] + H]+ 763.2097). CH), 3.78 (s, 3H, H12), 2.89−2.80 (m, 1H, cod-CH2), 2.64−2.54
4.3.2. Characterization of Complex [3]. Complex [3] was (m, 2H, cod-CH2), 2.50−2.42 (m, 1H, cod-CH2), 2.27 (s, 3H, H11),
obtained as an orange solid. Yield: 12 mg, 0.205 mmol (41%). 1H 2.21 (s, 3H, H10), 2.19−2.14 (m, 2H, cod-CH2), 2.07−2.01 (m, 1H,
NMR (400 MHz, THF-d8): δ (ppm) 6.70 (d, 3JHH = 1.1 Hz, 1H, H4), cod-CH2), 2.00−1.93 (m, 1H, cod-CH2). 13C{1H} NMR (101 MHz,
6.57 (d, 3JHH = 1.1 Hz, 1H, H5), 4.51−4.45 (m, 1H, cod-CH), 4.28− THF-d8, only resonances for the main component [6] are listed): δ
4.17 (m, 2H, cod-CH), 3.83−3.75 (m, 1H, cod-CH), 3.63 (s, 3H, (ppm) 188.1 (s, C2), 143.4 (s, C4), 137.1 (s, C9), 128.7 (s, C6),
H6) 2.69−2.63 (m, 1H, cod-CH2), 2.59−2.51 (m, 2H, cod-CH2), 128.2 (s, C7), 115.6 (s, C5), 109.9 (s, C8), 78.9 (d, 1JCRh = 3.9 Hz,
2.46−2.40 (m, 1H, cod-CH2), 2.21−2.13 (m, 2H, cod-CH2), 1.95− cod-CH), 78.7 (d, 1JCRh = 2.6 Hz), 73.6 (s, cod-CH), 72.0 (s, cod-
1.85 (m, 2H, cod-CH2). 13C{1H} NMR (101 MHz, THF-d8): δ CH), 33.24 (s, cod-CH2), 33.22 (s, C12), 32.8 (s, cod-CH2), 32.3 (s,
(ppm) 180.6 (d, 1JCRh = 50.5 Hz, C2), 127.1 (s, C4), 119.1 (s, C5), cod-CH2), 32.0 (s, cod-CH2), 20.5 (s C11), 20.2 (s, C10). HRMS
85.5 (d, 1JCRh = 7.7 Hz, cod-CH), 83.6 (d, 1JCRh = 8.4 Hz, cod-CH), (ESI, positive ions) m/z: 830.2405 [6]+ (calcd for [6]+ 830.2409).
80.4 (d, 1JCRh = 13.2 Hz, cod-CH), 77.0 (d, 1JCRh = 11.4 Hz, cod- 4.6. Synthesis of Complex [7]. Compound 1 (16 mg, 0.10
CH), 35.6 (s, C6), 32.4 (s, cod-CH2), 32.2 (s, cod-CH2), 31.9 (s, mmol) was dissolved in THF (5 mL) and the solution was cooled to
cod-CH2), 31.8 (s, cod-CH2). HRMS (ESI, positive ions) m/z: −78 °C. Then, n-BuLi (0.13 mmol, 0.08 mL of a 1.6 M solution in n-
584.0518 [3]+ (calcd for [3]+ 584.0894). hexane) was added. The reaction mixture was stirred for 2 h at −78
4.4. General Procedure for the Synthesis of Complexes [4] °C. Then, [Ir(cod)(μ-Cl)]2 (16.8 mg, 0.025 mmol) was added and
and [5]. Compound 1 (32.0 mg, 0.20 mmol) was dissolved in THF the solution was stirred over night while it was allowed to warm up to
(5 mL) and the solution was cooled to −78 °C. Then, n-BuLi (0.2 ambient temperature. The solvent was removed in vacuo and the solid
mmol, 0.13 mL of a 1.6 M solution in n-hexane) was added. The residue was dissolved in THF (2 mL). Addition of n-pentane led to
reaction mixture was stirred for 2 h at −78 °C. Subsequently, precipitation of a white solid. The suspension was filtered through
[Ir(cod)(μ-Cl)]2 (0.1 mmol, 67.2 mg) or [Rh(cod)(μ-Cl)]2 (0.10 Celite and the solvent was removed from the filtrate under reduced
mmol, 49.3 mg) was added and the solution was stirred for 12 h while pressure to give complex [7] as a reddish solid. Yield: 23 mg, 0.037
it was allowed to warm up to ambient temperature. The solvent was mmol, 74%. 1H NMR (400 MHz, THF-d8): δ (ppm) 6.93 (s, 1H,
removed in vacuo and the resulting residue was washed with H5), 6.80 (s, 1H, H8), 3.93 (s, 3H, H12), 3.91 (m, 1H, cod-CH),
methanol (2 × 5 mL) and dried under reduced pressure. 3.58 (m, 1H, cod-CH), 2.29 (m, 1H, cod-CH2), 2.22 (s, 3H, H11),
4.4.1. Characterization of Complex [4]. Complex [4] was 2.20 (s, 3H, H10), 2.05 (m, 1H, cod-CH2), 1.84 (m, 1H, cod-CH2),
obtained as a red solid. Yield: 41 mg, 45 mmol, 45%. 1H NMR 1.72 (m, 1H, cod-CH2). 13C{1H} NMR (101 MHz, THF-d8): δ
(400 MHz, THF-d8): δ (ppm) 7.40 (s, 1H, H5), 6.85 (s, 1H, H8), (ppm) 192.6 (s, C2), 144.0 (s, C4), 134.6 (s, C9), 123.8 (C6), 123.1
4.82 (s br, 1H, cod-CH), 4.43 (s br, 1H, cod-CH), 3.85 (s br, 1H, (s, C7), 113.3 (s, C5), 105.6 (s, C8), 68.9 (s, cod-CH), 67.0 (s, cod-
cod-CH), 3.80 (s, 3H, H12), 3.58 (s br, 1H, cod-CH), 2.68−2.60 (m, CH), 30.3 (s, C112), 29.7 (s, cod-CH2), 29.4 (s, cod-CH2), 17.42 (s,
1H, cod-CH2), 2.49−2.41 (m, 2H, cod-CH2), 2.36 (s, 1H, cod-CH2), C11), 17.40 (s, C10). 7Li NMR (155 MHz, THF-d8): δ (ppm) 1.6.
2.25 (s, 3H, H11), 2.22 (s, 3H, H10), 2.20−2.18 (m, 1H, cod-CH2), MS (ESI, positive ions) m/z: 621.2566 [7−Li + 2H]+ (calcd for [7−
2.15−2.13 (m, 1H, cod-CH2), 1.80−1.76 (m, 2H, cod-CH2). 13C{1H} Li + 2H]+ 621.2570). MS (MALDI-TOF, matrix DCTB) m/z: 621
NMR (101 MHz, THF-d8): δ (ppm) 185.5 (C2), 142.2 (C4), 136.9 [7−Li + 2H]+.
(C9), 129.0 (C6), 128.7 (C7), 115.6 (C5), 110.1 (C8), 74.4 (cod- 4.7. Synthesis of Complex [6] from [7]. A sample of complex
CH), 72.2 (cod-CH), 62.8 (cod-CH), 61.0 (cod-CH), 33.4 (C12), [7] (27.7 mg, 0.04 mmol) was dissolved in THF (5 mL) and
33.0 (cod-CH2), 32.9 (cod-CH2), 32.8 (cod-CH2), 32.7 (cod-CH2), [Rh(cod)(μ-Cl)]2 (10.8 mg, 0.02 mmol) was added as a solid. The
20.3 (C11), 20.1 (C10). MS (MALDI-TOF, matrix DCTB) m/z: 918 reaction mixture was stirred at ambient temperature for 12 h. The
[4]+. solvent was removed in vacuo and the solid residue was washed with
4.4.2. Characterization of Complex [5]. Complex [5] was methanol (2 × 5 mL) and dried under reduced pressure to give
obtained as an orange solid. Yield: 26 mg, 35 mmol, 35%. 1H NMR complex [6] as a reddish solid. Yield: 29.9 mg, 0.036 mmol, 90%. 1H
(400 MHz, THF-d8): δ (ppm) 7.36 (s, 1H, H5), 6.77 (s, 1H, H8), NMR (400 MHz, THF-d8): δ (ppm) 7.38 (s, 1H, H5), 6.81 (s, 1H,
5.08 (s br, 1H, cod-CH), 4.79 (s br, 1H, cod-CH), 4.50 (s br, 1H, H8), 5.11−5.03 (m, 1H, cod-CH), 4.47−4.40 (m, 1H, cod-CH),
cod-CH), 4.04 (s br, 1H, cod-CH), 3.82 (s, 3H, H12), 2.90−2.80 (m, 4.02−3.92 (m, 2H, cod-CH), 3.78 (s, 3H, H12), 2.87−2.81 (m, 1H,
1H, cod-CH2), 2.78−2.71 (m, 1H, cod-CH2), 2.69−2.60 (m, 1H, cod-CH2), 2.62−2.55 (m, 2H, cod-CH2), 2.50−2.42 (m, 1H, cod-
cod-CH2), 2.63−2.54 (m, 1H, cod-CH2), 2.37−2.29 (m, 2H, cod- CH2), 2.27 (s, 3H, H11), 2.21 (s, 3H, H10), 2.19−2.14 (m, 2H, cod-
CH2), 2.25 (s, 3H, H11), 2.19 (s, 3H, H10), 2.08−2.02 (m, 1H, cod- CH2), 2.08−2.01 (m, 1H, cod-CH2), 1.99−1.93 (m, 1H, cod-CH2).
CH2), 2.02−1.95 (m, 1H, cod-CH2). 13C{1H} NMR (101 MHz, 13
C{1H} NMR (101 MHz, THF-d8): δ (ppm) 188.1 (s, C2), 143.4 (s,
THF-d8): δ (ppm) 192.5 (d, 1JCRh = 49.8 Hz, C2), 143.6 (s, C4), C4), 137.1 (s, C9), 128.8 (s, C6), 128.2 (s, C7), 115.6 (s, C5), 109.9
136.5 (s, C9), 128.1 (s, C6), 127.6 (s, C7), 115.0 (s, C5), 109.2 (s, (s, C8), 78.9 (d, 1JCRh = 3.9 Hz, cod-CH), 78.7 (d, 1JCRh = 2.6 Hz,
C8), 87.2 (d, 1JCRh = 8.4 Hz, cod-CH), 86.6 (d, 1JCRh = 7.1 Hz, cod- cod-CH), 73.6 (s, cod-CH), 72.1 (s, cod-CH), 33.24 (s, cod-CH2),
CH), 78.2 (d, 1JCRh = 10.2 Hz, cod-CH), 78.1 (d, 1JCRh = 8.9 Hz, cod- 33.22 (s, C12), 32.8 (s, cod-CH2), 32.3 (s, cod-CH2), 32.0 (s, cod-
CH), 33.4 (s, C12), 32.2 (s, 2 × cod-CH2), 31.9 (s, cod-CH2), 31.7 CH2), 20.5 (s C11), 20.2 (s, C10). MS (MALDI-TOF, matrix
(s, cod-CH2), 20.3 (s, C11), 20.1 (s, C10). HRMS (ESI, positive DCTB) m/z: 831 [[6] + H]+.
ions) m/z: 531.1989 [[5]−Rh(cod) + 2H]+ (calcd for [[5]−Rh(cod) 4.8. General Procedure for the Synthesis of Complexes [8]
+ 2H]+ 531.1995). and [9]. Lithium diisopropylamide (16 mg, 0.15 mmol) was dissolved
4.5. Synthesis of the Complex Mixture [4]−[6]. Compound 1 in THF (4 mL) and the solution was cooled to −78 °C. The caffeine
(32.0 mg, 0.20 mmol) was dissolved in THF (5 mL) and cooled to (19.8 mg, 0.10 mmol) was added. The reaction mixture was stirred for
−78 °C. Then, n-BuLi (0.2 mmol, 0.13 mL of a 1.6 M solution in n- 2 h at −78 °C. Subsequently, [Ir(cod)(μ-Cl)]2 (33.6 mg, 0.05 mmol)
hexane) was added. The reaction mixture was stirred for 2 h at −78 or [Rh(cod)(μ-Cl)]2 (24.7 mg, 0.05 mmol) was added and the
°C. Subsequently, [Ir(cod)(μ-Cl)]2 (33.6 mg, 0.05 mmol) and solution was stirred for 12 h while it was allowed to warm up to
[Rh(cod)(μ-Cl)]2 (24.7 mg, 0.05 mmol) were added and the solution ambient temperature. The solvent was removed in vacuo and the solid
was stirred for 12 h while it was allowed to warm up to ambient residue was washed with methanol (2 × 2 mL) and dried under
temperature. The solvent was removed in vacuo and the resulting reduced pressure.
residue was washed with methanol (2 × 5 mL) and dried under 4.8.1. Characterization of Complex [8]. Yield: 14 mg, 0.014
reduced pressure. The mixture of complexes [4]−[6] was obtained as mmol, 28%, ratio [8H−H]/[8H−T] 50:50. 1H NMR (400 MHz, THF-
d8 for [8H−H]): δ (ppm) 4.67 (m, 2H, cod-CH), 4.22 (s, 6H, C-11), parameters against all |F2| with anisotropic thermal parameters for all
4.04 (m, 2H, cod-CH), 4.03 (s, 6H, H-12), 3.60 (m, 2H, cod-CH), non-hydrogen atoms and hydrogen atoms on calculated positions, R =
3.56 (m, 2H, cod-CH), 3.15 (s, 6H, H-10), 2.50 (m, 2H, cod-CH2), 0.0292, wR = 0.0686 [I ≥ 2σ(I)], R = 0.0381, wR = 0.0715 (all data).
2.46 (m, 2H, cod-CH2), 2.45 (m, 2H, cod-CH2), 2.43 (m, 2H, cod- The asymmetric unit contains one formula unit.
CH2), 2.30 (m, 2H, cod-CH2), 2.28 (m, 2H, cod-CH2), 1.76 (m, 2H, 4.9.2. Crystallographic Data for [5]·2C6H5F. Crystals suitable for
cod-CH2), 1.69 (m, 2H, cod-CH2). 13C{1H} NMR (101 MHz, THF- an X-ray diffraction study were obtained by cooling a concentrated
d8 for [8H−H]): δ (ppm) 182.6 (C-8), 154.6 (C-6), 152.6 (C-2), 147.4 solution of [5] in fluorobenzene. Formula C48H56N4F2Rh2, M =
(C-4), 110.6 (C-5), 78.7 (cod-CH), 74.7 (cod-CH), 63.2 (cod-CH), 932.78, red blocks, 0.22 × 0.14 × 0.12 mm3, triclinic, space group P1̅,
56.2 (cod-CH), 36.9 (C-12), 33.0 (cod-CH2), 32.8 (C-11), 32.5 a = 10.5486(2), b = 11.5988(2), c = 17.9751(3) Å, α = 85.6760(10),
(cod-CH2), 32.4 (cod-CH2), 32.1 (cod-CH2), 27.6 (C-10). 1H NMR β = 80.7610(10), γ = 70.8570(10), V = 2050.10(6) Å3, Z = 2, ρcalcd =
(400 MHz, THF-d8 for [8H−T]): δ (ppm) 4.53 (m, 2H, cod-CH), 1.511 g·cm−3, μ = 0.853 mm−1, 38 697 intensities measured in the
4.17 (s, 6H, H-11), 4.17 (m, 2H, cod-CH), 4.09 (s, 6H, H-12), 3.92 range 6.0° ≤ 2Θ ≤ 63.9°, 13 127 independent intensities (Rint =
(m, 2H, cod-CH), 3.56 (m, 2H, cod-CH), 3.15 (s, 6H, H-10), 2.60 0.0393), 10 400 observed intensities [I ≥ 2σ(I)], semiempirical
(m, 2H, cod-CH2), 2.53 (m, 2H, cod-CH2), 2.42 (m, 2H, cod-CH2), absorption correction (0.857 ≤ T ≤ 0.905), refinement of 489
2.32 (m, 2H, cod-CH2), 2.21 (m, 2H, cod-CH2), 2.10 (m, 2H, cod- parameters against all |F2| with anisotropic thermal parameters for all
CH2), 1.86 (m, 2H, cod-CH2), 1.76 (m, 2H, cod-CH2). 13C{1H} non-hydrogen atoms and hydrogen atoms on calculated positions, R =
NMR (101 MHz, THF-d8 for [8H−T]): δ (ppm) 178.6 (s, C-8), 154.6 0.0399, wR = 0.1031 [I ≥ 2σ(I)], R = 0.0554, wR = 0.1132 (all data).
(s, C-6), 152.6 (s, C-2), 147.4 (s, C-4), 110.7 (s, C-5), 81.2 (s, cod- The asymmetric unit contains one formula unit of complex [5] and
CH), 81.1 (s, cod-CH), 78.7 (s, cod-CH), 74.7 (s, cod-CH), 36.1 (s, two molecules of fluorobenzene. The fluorine atom of one molecule
C-12), 35.6 (s, cod-CH2), 33.6 (s, cod-CH2), 32.6 (s, cod-CH2), 32.5 of fluorobenzene is disordered over two positions (occupancies
(s, C-11), 29.3 (s, cod-CH2), 27.6 (s, C-10). MS (MALDI-TOF, 80:20). The entire second fluorobenzene molecule is disordered over
matrix DCTB) m/z (%): 986 (100) [8]+. two positions (occupancies 60:40) and the positional parameters for
4.8.2. Characterization of Complex [9]. Yield: 16 mg, 0.020 this molecule were refined with isotropic displacement parameters.
mmol, 40%, ratio [9H−H]/[9H−T] 30:70. 1H NMR (400 MHz, THF- No hydrogen positions were calculated for carbon atoms refined with
d8 for [9H−H]): δ (ppm) 5.01 (m, 2H, cod-CH), 4.66 (m, 2H, cod- isotropic displacement parameters.
CH), 4.33 (s, 6H, H-11), 4.32 (m, 2H, cod-CH), 4.06 (m, 2H, cod- 4.9.3. Crystallographic Data for [6]·2C6H5F. Crystals suitable for
CH), 4.03 (s, 6H, H-12), 3.11 (s, 6H, H-10), 2.76 (m, 2H, cod-CH2), an X-ray diffraction study were obtained by cooling a concentrated
2.73 (m, 2H, cod-CH2), 2.65 (m, 2H, cod-CH2), 2.62 (m, 2H, cod- solution of [6] in fluorobenzene. Formula C48H56F2Ir1.33N4Rh0.67, M =
CH2), 2.40 (m, 2H, cod-CH2), 2.40 (m, 2H, cod-CH2), 1.98 (m, 2H, 1051.54, purple plates, 0.443 × 0.300 × 0.113 mm3, triclinic, space
cod-CH2), 1.97 (m, 2H, cod-CH2). 13C{1H} NMR (101 MHz, THF- group P1̅, a = 10.5666(2), b = 11.5860(2), c = 17.9775(4) Å, α =
d8 for [9H−H]): δ (ppm) 188.7 (d, 1JRhC = 50.0 Hz, C-8), 153.8 (s, C- 85.8891(10), β = 80.7144(10), γ = 70.7500(10), V = 2050.20(7) Å3,
6), 152.5 (s, C-2), 148.7 (s, C-4), 110.2 (s, C-5), 90.8 (d, 1JRhC = 8.3 Z = 2, ρcalcd = 1.703 g·cm−3, μ = 4.630 mm−1, 37 179 intensities
Hz, cod-CH), 88.1 (d, 1JRhC = 7.0 Hz, cod-CH), 81.7 (d, 1JRhC = 13.5 measured in the range 5.9° ≤ 2Θ ≤ 61.1°, 12 420 independent
Hz, cod-CH), 80.1 (d, 1JRhC = 11.8 Hz, cod-CH), 36.7 (s, C-12), 33.0 intensities (Rint = 0.0347), 11 675 observed intensities [I ≥ 2σ(I)],
(s, cod-CH2), 32.1(s, C-11), 32.0 (s, cod-CH2), 31.7 (s, cod-CH2), semiempirical absorption correction (0.002 ≤ T ≤ 0.020), refinement
30.0 (s, cod-CH2), 27.3 (s, C-10). 1H NMR (400 MHz, THF-d8 for of 559 parameters against all |F2| with anisotropic thermal parameters
[9H−T]): δ (ppm) 4.73 (m, 2H, cod-CH), 4.66 (m, 2H, cod-CH), for all non-hydrogen atoms and hydrogen atoms on calculated
4.33 (s, 6H, H-11), 4.54 (m, 2H, cod-CH), 4.06 (s, 6H, H-12), 3.96 positions, R = 0.0444, wR = 0.1162 [I ≥ 2σ(I)], R = 0.0460, wR =
(m, 2H, cod-CH), 3.12 (s, 6H, H-10), 2.76 (m, 2H, cod-CH2), 2.69 0.1182 (all data). The asymmetric unit contains 1 formula unit of
(m, 2H, cod-CH2), 2.63 (m, 2H, cod-CH2), 2.55 (m, 2H, cod-CH2), complex [6], and two molecules of fluorobenzene. Complex [6] had a
2.26 (m, 2H, cod-CH2), 2.16 (m, 2H, cod-CH2), 2.14 (m, 2H, cod- Rh/Ir substitutional disorder (occupancies Rh/Ir, 67:33) and the
CH2), 2.14 (m, 2H, cod-CH2). 13C{1H} NMR (101 MHz, THF-d8 positional and anisotropic displacement parameters of the disordered
for [9H−T]): δ (ppm) 183.2 (d, 1JRhC = 48.2 Hz, C-8), 154.0 (s, C-6), Rh and Ir atoms were constrained to be the same. The fluorine atoms
152.6 (s, C-2), 148.5 (s, C-4), 110.2 (s, C-5), 95.8 (d, 1JRhC = 6.9 Hz, of both fluorobenzene molecules are disordered over two positions.
cod-CH), 95.0 (d, 1JRhC = 7.5 Hz, cod-CH), 75.9 (d, 1JRhC = 14.4 Hz, 4.9.4. Crystal Data for Complex [9H−T]·C4H8O. Crystals suitable
cod-CH), 72.2 (d, 1JRhC = 12.1 Hz, cod-CH), 35.8 (s, C-12), 33.0 (s, for an X-ray diffraction study were obtained by slow diffusion of n-
cod-CH2), 32.9 (s, cod-CH2), 32.5 (s, C-11), 32.5 (s, cod-CH2), 29.8 hexane into a saturated solution of the complex mixture [9H−T]/
(s, cod-CH2), 27.3 (s, C-10). MS (MALDI-TOF, matrix DCTB) m/z [9H−H] in THF. Formula C36H50N8O5Rh2, M = 880.66, orange
(%): 808 (75) [9]+, 700 (100) [9−cod]+. needles, 0.360 × 0.260 × 0.100 mm3, triclinic, space group P1̅, a =
4.9. X-ray Diffraction Studies. X-ray diffraction data were 12.1104(5), b = 12.4776(5), c = 13.3350(5) Å, α = 76.316(2), β =
collected at T = 153 K for [3], [5]·2C6H5F and [6]·2C6H5F and at T 63.622(2), γ = 87.914(2), V = 1748.52(12) Å3, Z = 2, ρcalcd = 1.673 g·
= 100 K for [9H−T] using a Bruker AXS APEX II charge-coupled cm−3, μ = 1.000 mm−1, 47 891 intensities measured in the range 6.5°
device diffractometer equipped with a microsource using graphite- ≤ 2Θ ≤ 59.2°, 9746 independent intensities (Rint = 0.0325), 8651
monochromated Mo Kα radiation (λ = 0.71073 Å). Semiemperical observed intensities [I ≥ 2σ(I)], semiempirical absorption correction
multiscan absorption corrections were applied to all data sets.18 (0.673 ≤ T ≤ 0.745), refinement of 490 parameters against all |F2|
Structure solutions were found with SHELXT (intrinsic phasing)19a with anisotropic thermal parameters for all non-hydrogen atoms and
and were refined with SHELXL19b against |F2| of all data using first hydrogen atoms on calculated positions, R = 0.0274, wR = 0.0604 [I
isotropic and later anisotropic thermal parameters for all non- ≥ 2σ(I)], R = 0.0330, wR = 0.0627 (all data). The asymmetric unit
hydrogen atoms. Hydrogen atoms were added to the structure models contains one formula unit of [9H−T] and one THF molecule.
■
on calculated positions.
4.9.1. Crystallographic Data for [3]. Crystals suitable for an X-ray
diffraction study were obtained by cooling a concentrated solution of ASSOCIATED CONTENT
[3] in fluorobenzene. Formula C24H34N4Rh2, M = 584.37, orange *
S Supporting Information
plates, 0.173 × 0.097 × 0.004 mm3, triclinic, space group P1̅, a =
The Supporting Information is available free of charge on the
9.8190(2), b = 9.9553(2), c = 12.5831(2) Å, α = 76.9880(10), β =
89.2410(10), γ = 70.0240(10), V = 1123.60(4) Å3, Z = 2, ρcalcd = ACS Publications website at DOI: 10.1021/acs.organo-
1.727 g·cm−3, μ = 1.487 mm−1, 20 499 intensities measured in the met.9b00074.
range 5.7° ≤ 2Θ ≤ 62.0°, 7005 independent intensities (Rint = 1
H NMR and 13C{1H} NMR spectra of all new
0.0289), 5885 observed intensities [I ≥ 2σ(I)], semiempirical
absorption correction (0.824 ≤ T ≤ 0.890), refinement of 294 compounds (PDF)
Accession Codes Ligands. Chem.Eur. J. 2008, 14, 10900−10904. (e) Hahn, F. E.;
CCDC 1895429−1895432 contain the supplementary crys- Radloff, C.; Pape, T.; Hepp, A. A Nickel(II)-Cornered Molecular
tallographic data for this paper. These data can be obtained Rectangle with Biscarbene and 4,4′-Bipyridine Bridging Groups.
free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by Organometallics 2008, 27, 6408−6410. (f) Radloff, C.; Weigand, J. J.;
emailing data_request@ccdc.cam.ac.uk, or by contacting The Hahn, F. E. A Tetranuclear Molecular Rectangle from Four Gold(I)
Atoms Linked by Dicarbene and Diphosphine Ligands. Dalton Trans.
Cambridge Crystallographic Data Centre, 12 Union Road,
2009, 9392−9394. (g) Schmidtendorf, M.; Pape, T.; Hahn, F. E.
Cambridge CB2 1EZ, UK; fax: +44 1223 336033. Stepwise Preparation of a Molecular Square from NR,NR- and NH,O-
CCDC 1895429−1895432 contain the supplementary Substituted Dicarbene Building Blocks. Angew. Chem., Int. Ed. 2012,
crystallographic data for this paper. These data can be 51, 2195−2198. (h) Schmidtendorf, M.; Pape, T.; Hahn, F. E.
obtained free of charge via www.ccdc.cam.ac.uk/data_ Molecular Rectangles from Platinum(II) and Bridging Dicarbene,
request/cif, or by emailing data_request@ccdc.cam.ac.uk, or Diisocyanide and 4,4’-Bipyridine Ligands. Dalton Trans. 2013, 42,
by contacting The Cambridge Crystallographic Data Centre, 16128−16141. (i) Schmidtendorf, M.; Schulte to Brinke, C.; Hahn, F.
12 Union Road, Cambridge CB2 1EZ, UK, fax: +44 1223 E. Benzodicarbene-bridged dinuclear complexes as building blocks for
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620−627.
AUTHOR INFORMATION (4) (a) Enders, D.; Niemeier, O.; Henseler, A. Organocatalysis by N-
Heterocyclic Carbenes. Chem. Rev. 2007, 107, 5606−5655.
Corresponding Author (b) Marion, N.; Díez-González, S.; Nolan, S. P. N-Heterocyclic
*E-mail: fehahn@uni-muenster.de. Carbenes as Organocatalysts. Angew. Chem., Int. Ed. 2007, 46, 2988−
ORCID 3000. (c) Grossmann, A.; Enders, D. N-Heterocyclic Carbene
F. Ekkehardt Hahn: 0000-0002-2807-7232 Catalyzed Domino Reactions. Angew. Chem., Int. Ed. 2012, 51,
314−325. (d) Bugaut, X.; Glorius, F. Organocatalytic Umpolung: N-
Notes Heterocyclic Carbenes and Beyond. Chem. Soc. Rev. 2012, 41, 3511−
The authors declare no competing financial interest.
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3522. (e) De Sarkar, S.; Biswas, A.; Samanta, R. C.; Studer, A.
Catalysis with N-Heterocyclic Carbenes under Oxidative Conditions.
ACKNOWLEDGMENTS Chem.Eur. J. 2013, 19, 4664−4678.
The authors gratefully acknowledge financial support from the (5) (a) Herrmann, W. A. N-Heterocyclic Carbenes: A New Concept
Deutsche Forschungsgemeinschaft (SFB 858 and IRTG 2027). in Organometallic Catalysis. Angew. Chem., Int. Ed. 2002, 41, 1290−
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