Hexa-: Peri-hexabenzocoronene decorated with an allenylidene ruthenium complex-Almost a flyswatter

Article abstract of DOI:10.1039/d0dt02729d

Carbon-rich ruthenium allenylidene complexes bearing either a hexaarylbenzene (HAB) or a hexa-peri-hexabenzocoronene (HBC) substituent were synthesised. This was achieved via the corresponding propargyl alcohols with HAB and HBC substituents, which were accessible via 3 or 4 step reaction cascades. Reaction of the propargyl alcohols HCC(OH)Ph(HAB) and HCC(OH)Ph(HBC) with [RuCl(η5-C5H5)(PPh3)2] yielded the complexes [Ru(η5-C5H5)(CCC(HAB)(Ph))(PPh3)2]PF6 and [Ru(η5-C5H5)(CCC(HBC)(Ph))(PPh3)2]PF6. The latter of which shows interesting π-π-stacking behaviour in the solid state as well as aggregation in solution.

Full text of DOI:10.1039/d0dt02729d

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DOI: 10.1039/D0DT02729D
ARTICLE
Hexa-peri-hexabenzocoronene decorated with an allenylidene
‡
ruthenium complex – almost a flyswatter
Rebecca Lorenz,a David Reger,b Ruth Weller,ac Norbert Jux *b and Nicolai Burzlaff*a
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Carbon-rich ruthenium allenylidene complexes bearing either a conducted, however to the best of our knowledge no HBC full-
hexaarylbenzene (HAB) or a hexa-peri-hexabenzocoronene (HBC) sandwich complex was reported until now.9 Moreover, it was
substituent were synthesised. This was achieved via the possible to attach ferrocenyl units via an alkynyl bridge to a
corresponding propargyl alcohols with HAB and HBC substituents, HBC.10 It was also shown that new triarylphosphine ligands can
which were accessible via 3 or 4 step reaction cascades. Reaction be designed by using HBC units.11 A different approach showed
of
the
propargyl
alcohols
HC≡C(OH)Ph(HAB)
and that HBCs can be modified with N,N-chelating motifs that can
HC≡C(OH)Ph(HBC) with [RuCl(5-C5H5)(PPh3)2] yielded the coordinate ruthenium, palladium and rhenium fragments.12
complexes [Ru(5-C5H5)(=C=C=C(HAB)(Ph))(PPh3)2]PF6 and [Ru(5- Furthermore, -bonded platinum complexes have been
C5H5)(=C=C=C(HBC)(Ph))(PPh3)2]PF6. The latter of which shows synthesised by EL HAMAOUI et al.13 Acetylene units can also
interesting --stacking behaviour in the solid state as well as serve as a connection point between metal fragments and
aggregation in solution.
HBC. Several platinum and gold complexes were synthesised
following this concept.14 Furthermore, acetylene complexes
derived from dicobalt octacarbonyl have been reported.15
In recent years, various research groups focused on the
synthesis and investigation of ruthenium allenylidene
complexes.17,18,19 Our group reported on a panoply of these
complexes [Ru]=C=C=CR2, either with the charge neutral
[Ru(bdmpza)Cl(PPh3)] fragment (bdmpza = bis(3,5-dimethyl-
pyrazol-1-yl)acetate) or the cationic [Ru(5-C5H5)(PPh3)2]+
fragment.20–23 The synthesis of these ruthenium allenylidene
complexes follows a synthetic concept published by SELEGUE
(Scheme 1).16
Hexa-peri-hexabenzocoronenes (HBCs) are all benzenoid
polycyclic aromatic hydrocarbons (PAHs) with remarkable
properties, such as an impressive chemical and thermal
stability.1,2 The unsubstituted HBC aggregates in a columnar
fashion, which makes them promising candidates for the
application as charge transport layers in various electronic
devices.2,3 Since the first synthesis of the parent HBC by CLAR
and co-workers back in 1958, sophisticated synthetic
procedures have been developed to obtain a large variety of
HBCs.1,4 Hexa(alkyl)-HBCs undergo facile self-assembly into
columnar mesophases with high charge carrier mobility.5 Their
behaviour as semiconducting organic materials makes these
molecules suitable candidates for the application in organic
field-effect transistors (OFETs) and as donor materials in
organic photovoltaics (OPVs).6
PF6
R'
NH4[PF6]
Ru
OH
+
Ru
Cl
Ph3P
Ph3P
•
EtOH
 H2O
Ph3P
PPh3
R
•
R'
R
Inspired by this, several transition metal complex decorated
HBCs have been synthesised and the interactions between the
-systems and the metal centres have been studied during the
last decade. Among the first examples was a chromium
tricarbonyl HBC half-sandwich complex by HERWIG et al.7 In
analogy to this complex, several half-sandwich HBC rhodium
complexes have been reported.8 DFT calculations for
chromium and ruthenium sandwich complexes have been
R
R'
OH
Ru
Ph3P
Ph3P
•
H
Scheme 1 Synthesis of allenylidene in analogy to the procedure developed by
SELEGUE.16 R = Ph, R’ = HBC, HAB.
The focus in these studies lay on allenylidene complexes with
carbon-rich and/or polycyclic aromatic substituents R and was
mainly driven by interesting possible applications in molecular
electronics24 and novel opto-electronic materials19. Also other
groups showed that the combination of allenylidene
complexes and carbon-rich fragments, for instance, the
conjunction with fullerenes, leads to new molecules with
a. Department Chemistry and Pharmacy, Interdisciplinary Center of Molecular
Materials (ICMM), University of Erlangen-Nuernberg, Egerlandstr. 1, 91058
Erlangen, Germany.
b. Department Chemistry and Pharmacy, University of Erlangen-Nuernberg,
Nicolaus-Fiebiger-Str. 10, 91058 Erlangen, Germany.
c. Fb. 15 – Chemie, Philipps-University Marburg, Hans-Meerwein-Straße 4, 35032
Marburg, Germany.
† Electronic supplementary information (ESI) available: Experimental details, X-ray
crystallographic data for
6 and NMR spectra for all new compounds. See
DOI: 10.1039/x0xx00000x
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diverse properties.25 Due to possible synergistic effects procedures.27–29 Branching off at that point the propargyl
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between these properties and those of HBC, we were now alcohol of HAB 4 was obtained by nuclDeOoIp: h10il.i1c03a9d/Dd0itDioT0n27o2f9Da
interested in the synthesis of allenylidene complexes with a trimethylsilylacetylene anion followed by an in situ desilylation
HBC as substituent R (Scheme 1).
reaction. By applying the procedure reported by SELEGUE, the
Thus, herein we report on the synthesis and characterisation desired deep purple allenylidene complex [Ru(5-
of two novel carbon-rich ruthenium allenylidene complexes C5H5)(=C=C=C(HAB)(Ph))(PPh3)2]PF6 (5) was obtained. By
bearing either a HAB or a HBC moiety. To prepare these oxidative closure of 3 under SCHOLL conditions, HBC 6 was
compounds the reaction procedure introduced by SELEGUE was prepared. The propargyl alcohol 7 was synthesised in analogy
adapted (Scheme 1). As this reaction route is a wet-chemical to compound 4. The desired dark green-blue allenylidene
approach a t-butylated HBC was used to ensure sufficient complex [Ru(5-C5H5)(=C=C=C(HBC)(Ph))(PPh3)2]PF6 (8) was
solubility.26 In order to demonstrate the influence of the obtained in analogy to complex 5. The yields of the
conjugated -system of the HBC the corresponding HAB allenylidene complexes 5 and 8 are rather low due to
complex was synthesised as well. The required propargyl purification of the cationic complexes by column
alcohols were synthesised following a 3 or 4 step procedure, chromatography, which is a lossy procedure. The 13C NMR
depicted in Scheme 2. The reaction cascade starts from spectra of both allenylidene complexes 5 and 8 show the
commercially available 4-bromobenzophenone 1. The characteristic signal of C in the downfield region at 290.5 and
precursor was converted into the acetylene derivative 2 via a 290.7 ppm, respectively. Due to the 2J coupling with the
SONOGASHIRA coupling followed by a DIELS-ALDER reaction with phosphorous nuclei, both signals split into triplets with
tetrakis-(4-tert-butylphenyl)cyclopentadienone to obtain HAB- coupling constants of 18 Hz. Both values are in good
benzophenone derivative 3. Tetrakis-(4-tert-butylphenyl)cyclo- agreement with the already reported ones.23 Interestingly, the
pentadienone was synthesised according to literature nature of the PAH residue on C does not seem to have a large.
O
O
a)
Br
1
2
b)
PF6
O
OH
e)
d)
Ru
•
Ph3P
Ph3P
•
3
4
5
c)
PF6
O
OH
e)
d)
Ru
•
Ph3P
Ph3P
•
7
6
8
Scheme 2 Synthesis of complexes 5 and 8: a) 4-tert-butylphenylacetylene (1.05 eq.), Pd(PPh3)2Cl2 (2 mol%), CuI (1 mol%), THF/DIPA 1:1; b) tetrakis-(4-tert-
butylphenyl)cyclopentadienone (1.00 eq.), toluene; c) FeCl3 (16 eq.) in MeNO2 (300 mg/mL), CH2Cl2; d) trimethylsilylacetylene (10 eq), n-BuLi (10 eq) in THF; e)
[Ru(5-C5H5)Cl(PPh3)2] (1.00 eq), NH4[PF6] (1.00 eq), MeOH
2 | J. Name., 2012, 00, 1-3
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influence on the chemical shift of C. Since this chemical shift are intercalated.7 Within one dimer the arrangement is similar
View Article Online
DOI: 10.1039/D0DT02729D
directly correlates with the contribution of the allenylidene to the one adopted by two layers of graphene (interplanar
versus the alkynyl resonance structure (Scheme 3), it can be distance: 3.35 Å),30 where one carbon atom is projected to the
concluded that the nature of the cumulene chain is similar in middle of the six-membered ring of the neighbouring layer
both complexes.
(Fig. 2).31
R

R
R


[M] C C
[M] C C
[M] C C C


 


Scheme
3 Limiting resonance structures and conventional designation in
allenylidene complexes.17,18d,19 Right: allenylidene; left: alkynyl form. Further
delocalisation over the aromatic and polyaromatic residues at C is possible. R =
PAH.
The bond lengths obtained from crystal structure analysis of
compound 8 show the characteristic elongation of the RuC
and CC bond due to a significant single bond contribution
(Fig. 1).‡ This results in a shortened C-C bonds due to the
triple bond character of this bond. Comparison with literature
known allenylidene complexes substantiates the pronounced
contribution of the alkynyl structure. The ideal angle of the
cumulene chain (Ru-C-C and C-C-C) is 180°. However,
the measured angles are 171.2(2) and 169.3(3)°, respectively.
This deviation might be due to the steric hindrance provided
by the HBC moiety and the flexibility of both groups attached
to C. Similar deviations were observed for large rigid organic
substituents, before.20,22,23
Fig. 2 Packing motif of 8. Dimer formation due to --stacking. Interplanar
distance is 3.592 Å.
The UV/Vis absorption spectrum of [Ru(5-C5H5)(=C=C=C(HAB)
(Ph))(PPh3)2]PF6 (5) shows an absorption maximum in the near-
UV region at 252 nm (63700 L mol1 cm1), which is
characteristic for such non-planar structures. Additionally, a
small absorption band is located at 340 nm (9200 L mol1 cm1)
and another maximum is observed at 532 nm
(30600 L mol1 cm1) (Fig. 3). The latter one is usually assigned
to a metal perturbed -*transition of the allenylidene unit.17
The shift of this transition is similar to the one of a simple
diphenyl allenylidene complex bearing a trispyrazolylborate
(Tp) ligand [Ru(=C=C=C(Ph)2)(PPh3)2(Tp)]SbF6, which is
detected at 527 nm.32
In contrast, [Ru(5-C5H5)(=C=C=C(HBC)(Ph))(PPh3)2]PF6 (8)
shows an absorption throughout the visible spectrum. The
highest extinction coefficient (33300 L mol1 cm1) is observed
for the absorption maximum at 359 nm.
Fig. 1 Molecular structure of 8. Thermal ellipsoids are shown at a 50% probability
level. Hydrogen atoms, solvent molecules and hexafluorophosphate anion are
omitted for clarity. Only majority positions are shown for clarity. Selected bond
lengths (Å) and angles (°): Ru-P1 2.3462(8), Ru-P2 2.3162(8), CCp-Ru 1.8975(1),
Ru-C 1.897(3), C-C 1.255(4), C-C 1.357(4), P1-Ru-P2 97.60(3), Ru-C-C
171.2(2), C-C-C 169.3(3).
The investigation of the packing motif reveals the formation of
a dimer with interplanar distances of 3.592 Å (Fig. 2). The
ruthenium units are located on opposing sites in the dimer.
Furthermore, the t-butyl groups point to the periphery of the
dimer which leads to an out-of-plane bending of the HBC
moiety. The most significant deviation from the planar
arrangement amounts to 0.788 Å. This deviation is measured
from the central six-membered ring plane to the central atom
of the t-butyl group (C43). A similar behaviour has already
been observed for the simple t-butyl substituted HBC. The
parent HBC molecule shows a slightly smaller interplanar
distance of 3.44 Å. Between pairs of dimers solvent molecules
Fig. 3 UV/Vis absorption spectra of 5 and 8 in CH2Cl2 (245-1100 nm).
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The characteristic maxima of the HBC unit are located at −0.863 and −1.94 V, respectively and exVhieiwbAitrticlqe uOnalsinie-
between 343 and 382 nm.2 Interestingly, two additional reversible character. They might correspond to two one
DOI: 10.1039/D0DT02729D
absorption bands are observed at 495 and 636 nm (Fig. 3). electron reductions of the allenylidene unit or to the reduction
These maxima correspond to metal-perturbed -* transitions of the organic ligand.
of the allenylidene moiety. In comparison with the simple The measurements of complex 8 revealed one reduction and
diphenyl and the HAB decorated allenylidene complex 5, this one oxidation process (Fig. 5, Fig. S32-S34). The oxidation
maximum experiences a significant bathochromic shift.
event shows an irreversible process at 1.02 V. Multiple scans
In order to investigate the aggregation behaviour in solution, of the high potential region led to the disappearance of the
UV/Vis titration experiments with pyrene were conducted. The oxidation sweep. A similar behaviour has already been
resulting JOB’s plots show a maximum at R = 0.5, which observed for thienyl-substituted ruthenium allenylidene
indicates the formation of a 1:1 aggregate, for complex 5 complexes.34 In this case, the oxidation was assigned to
(Fig. 4). The plot of complex 8 reveals a different shape. Two happen at the organic ligand and not as often reported at the
maxima at R = 0.4 and 0.65 (Fig. 4) can be observed. These metal centre.22,23,32,33 Due to the analogous behaviour, a
values indicate the formation of 1:2 and 2:1 aggregates in ligand-centred oxidation is assumed for HBC-based ruthenium
solution. This leads to the assumption that in solution either allenylidene complex 8. The reduction wave at −1.26 V exhibits
aggregates of two HBC moieties are formed compared to a quasi-reversible character. By comparing this value to other
those in the solid state, between those dimers an additional ruthenium allenylidene complexes, it can be readily assigned
pyrene molecule can be incorporated, or oligomeric chains are to the reduction of the allenylidene moiety.22,23
formed with alternating HBC dimers and pyrene moieties.
Fig. 5 Cyclic voltammogram of 5 (top) and 8 (bottom) (0.001 M) on a Au electrode
(0.1 V s1, 0.2 M n-Bu4NPF6/CH2Cl2, referenced to internal Fc+/Fc). * marks the
redox sweep of the Fc+/Fc reference redox couple.
Fig. 4 Job’s plots of the aggregation of 5 and 8 with pyrene in CH2Cl2. A was
calculated from variation in absorption maximum at 532 nm and 636 nm,
respectively.
In summary, we synthesised two novel carbon-rich ruthenium
complexes in a 5 and 6 step reaction cascade. The HBC
complex 8 is, to the best of our knowledge, an allenylidene
complex with one of the most extended conjugated systems.
The planarisation of the -system seems to have a major
influence on the aggregation properties. Furthermore,
To investigate and compare the electrochemical properties of
complex 5 and 8 cyclic voltammetry was conducted. For
complex 5 one oxidation and two reduction processes could be
observed (Fig. 5, Fig. S29-31). The oxidation event occurs at
0.896 V and may correspond to the Ru(II)/Ru(III)
oxidation.22,23,32,33 The two reduction processes are observed
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absorption and electrochemical properties were examined and 4G UHR MS/MS spectrometer or a Bruker micrOToF II focus
View Article Online
DOI: 10.1039/D0DT02729D
discussed. By fully conjugating the polycyclic aromatic system, ToF MS spectrometer. ESI MS spectra were recorded on an
it is possible to vary and broaden the absorption properties UHR time-of-flight (ToF) Bruker Daltonik maXis plus 5G, an ESI-
significantly.
quadrupole time-of-flight (q-ToF) MS capable of resolution of
at least 60.000 FWHM. The flow rates were 180 L/h. The
This work was generously supported by ‘Solar Technologies go machine was calibrated prior to each experiment via direct
Hybrid’, an initiative of the Bavarian State Ministry for Science, infusion of the Agilent ESI-ToF low concentration tuning
Research and Art. Funding of a Bruker AVANCE III HD 400 MHz mixture, which provided a m/z range of the singly charged
spectrometer and
spectrometer as well as
a
Bruker AVANCE III HD 600 MHz peaks up to 2700 Da. Peaks were identified using simulated
Super Nova S2 (Dual) isotopic patterns create by Bruker Data Analysis software.
a
A
diffractometer with Atlas S2 CCD detector and Nova (Cu) and Cyclic voltammetry experiments were carried out using a
Mova (Mo) X-ray sources by the German Research Council Methrom Autolab PGSTAT 100. A three-electrode setup was
(DFG) is gratefully acknowledged. Partly funded by the used, using a gold disk working electrode, a platinum wire
Deutsche Forschungsgemeinschaft (DFG) – Projektnummer counter electrode, and a silver wire as a pseudo-reference
182849149 – SFB 953. D.R. and R.L. thank the Graduate School electrode.
Molecular Science (GSMS) for financial support.
Synthetic procedures
4-(4-tert-butylphenylacetylene)benzophenone (2)
Experimental details
A round-bottom pressure-flask (100 mL) equipped with a
Materials and methods
magnetic stirring bar was charged with 4-bromobenzophenone
1 (2.00 g, 7.66 mmol), [Pd(PPh3)2Cl2] (0.110 g, 0.150 mmol), CuI
(15.2 mg, 0.0800 mmol), THF (25 mL) and diisopropylamine
(25 mL). The mixture was degassed by N2 bubbling for 10 min.
4-tert-butylphenylacetylene (1.27 g, 1.45 mL, 8.04 mmol) was
added and the flask was closed. The reaction mixture was
stirred for 18.5 h at 100 °C. After completion of the reaction all
solvents were removed under reduced pressure and the
remaining solids were purified by column chromatography
(silica, hexanes/CH2Cl2 1:2 v/v). All fractions containing the
product were collected, the solvents were evaporated and the
remaining brownish solid was recrystallized from hot n-
pentane (30 mL).The product was dried under vacuum and
was obtained as a white solid with a yield of 78 % (1.99 g,
5.88 mmol).
1H NMR (CDCl3, 400 MHz, rt.): δ [ppm] = 7.79–7.77 (m, 4H),
7.62–7.56 (m, 3H), 7.50–7.46 (m, 4H), 7.39–7.37 (m, 2H), 1.32
(s, 9H).
13C{1H} NMR (CDCl3, 100 MHz, rt.): δ [ppm] = 195.9, 152.2,
137.5, 136.6, 132.5, 131.5, 131.4, 130.1, 130.0, 128.3, 127.9,
125.5, 119.7, 92.8, 88.1, 34.9, 31.2.
HRMS (APPI, CH2Cl2): m/z = 339.1754 [M+H]+. Calculated:
339.1743.
All air-sensitive compounds were prepared under a dry N2 or
Ar atmosphere using conventional SCHLENK techniques. The
solvents were purchased from Sigma-Aldrich, Roth, Fluka or
Fisher Scientific (p.a. grade, < 50 ppm H2O). Solvents were
degassed prior to use and stored under N2 or Ar atmosphere
over molecular sieves. Tetrakis-(4-tert-butylphenyl)cyclo-
pentadienone was synthesised following known literature
procedures.27–29 All commercially available substances were
purchased from Sigma-Aldrich or abcr and used without
further purification. Thin layer chromatography (TLC) was
performed on Merck or Macherey-Nagel silica 60 F254,
detected by UV-light (254 nm, 366 nm). H NMR, 13C{1H} NMR,
1
APT 13C{1H} NMR and 31P{1H} NMR spectra were measured
with a JEOL JNM EX 400 MHz, JEOL JNM GX 400 MHz, Bruker
Avance 400 MHz, Bruker AVANCE III HD 400 MHz and Bruker
AVANCE III HD 600 MHz instrument. The  values are given in
ppm relative to tetramethylsilane and were referenced by the
solvent peaks of the deuterated solvent. For 31P{1H} NMR
spectra H3PO4 was used as an internal standard. The
resonance multiplicities are indicated as “s“ (singlet), “d”
(doublet), “t” (triplet), “q” (quartet), “sept” (septet) and “m”
(multiplet). Signals referred to as bs (broad singlet) are not
clearly resolved or significantly broadened. Para-substituted
phenyl rings with an AA’BB’ spin system are termed as
multiplets. IR spectra were recorded with a Bruker Alpha FT-IR
spectrometer equipped with Alpha’s Platinum ATR single
reflection diamond ATR module. IR spectra in solution were
measured in CaF2 cuvettes (0.2 mm) with a Jasco FT-IR 4100 or
a Shimadzu IRTracer-100. LDI/MALDI-ToF mass spectrometry
was performed on a Shimazu AXIMA Confidence (nitrogen
laser, 50 Hz, 337 nm). In case of MALDI, the following matrix
were used: 2,5-dihydroxybenzoic acid (DHB), sinapic acid (SIN)
HAB-benzophenone derivative 3
A round-bottom pressure-flask (250 mL) equipped with a
magnetic stirring bar was charged with 4-(4-tert-
butylphenylacetylene)benzophenone 2 (1.00 g, 2.95 mmol),
tetrakis-(4-tert-butylphenyl)cyclo-pentadienone
(1.80 g,
2.95 mmol) and toluene (15 mL). The flask was purged with N2
and was closed. The mixture was stirred for 60 h at 220 °C.
After completion of the reaction MeOH (50 mL) was added and
a white solid precipitated. The white solid was filtered off,
washed with an excess of MeOH and dried under vacuum. The
product was obtained in a yield of 71 % (1.90 g, 2.07 mmol).
1H NMR (CDCl3, 400 MHz, rt.): δ [ppm] = 7.53–7.51 (m, 2H),
7.50–7.46 (m, 1H), 7.36–7.32 (m, 2H), 7.29–7.27 (m, 2H), 6.98–
or
trans-2-[3-(4-tert-butylphenyl)-2-methyl-2-
propenylidene]malononitrile (DCTB). High resolution mass
spectrometry was performed on an Electrospray-ionization
mass spectrometry ESI-ToF mass spectrometer Bruker maXis
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6.96 (m, 2H), 6.85–6.83 (m, 4H), 6.82–6.79 (m, 6H), 6.71–6.64 The product was isolated in a yield of 17V%iew A(2rti9cl.e0Omnlinge,
DOI: 10.1039/D0DT02729D
(m, 10H), 1.12 (s, 18H), 1.08 (s, 27H).
16.4 µmol).
13C{1H} NMR (CDCl3, 100 MHz, rt.): δ [ppm] = 196.9, 147.9, 1H NMR (CD2Cl2, 600 MHz, rt.):  [ppm]  7.60 (t, 1H,
147.54, 147.51, 146.2, 141.0, 140.7, 139.9, 138.8, 138.0, 137.7, 3JH,H = 7.4 Hz, p-PhH), 7.33–7.28 (m, 8H, CArH), 7.26–7.23 (m,
137.6, 137.4, 133.8, 132.0, 131.5, 131.1, 131.0, 129.8, 128.5, 5H, CArH) 7.06 (t, 12H, JH,H = 7.3, m-PPh3), 7.03–6.99 (m, 13H,
3
3
128.0, 123.4, 123.11, 123.07, 34.1, 34.0, 31.21, 31.16.
o-PPh3, 1×CArH), 6.88 (d, 4H, JH,H = 8.2, CArH), 6.83 (t, 6H,
MS (MALDI-ToF, dhb): m/z = 919 [M]+, 942 [M+Na]+, 958 3JH,H = 7.7, p-PPh3), 6.79 (d, 4H, JH,H = 8.2, CArH), 6.70 (d, 2H,
3
[M+K]+.
3JH,H = 8.1, CArH), 6.67 (d, 4H, JH,H = 8.2, CArH), 4.96 (s, 5H,
3
HRMS (APPI, toluene): m/z = 918.57286 [M]+. Calculated: CCpH), 1.10 (s, 27H, 3×C(CH3)3), 1.06 (s, 18H, 2×C(CH3)3).
918.57342.
13C{1H} NMR (CD2Cl2, 151 MHz, rt.):  [ppm]  290.5 (t,
2JC,P = 18.3 Hz, C), 204.5 (C), 161.1 (C), 148.8 (CAr), 148.5
(CAr), 148.5 (CAr), 147.7 (CAr), 144.3 (i-Ph), 141.8 (CAr), 141.4
(CAr), 140.4 (CAr), 140.0 (CAr), 139.2 (CAr), 138.1 (CAr), 138.0
(CAr), 137.9 (CAr), 135.5–135.1 (m, i-PPh3), 133.4 (t,
3JC,P = 5.0 Hz, o-PPh3), 133.1 (CArH), 132.0 (CArH), 131.5
(2×CArH), 131.3 (2×CArH), 131.3 (CArH), 130.9 (p-PPh3), 130.6
HAB-Phenylpropargyl alcohol 4
TMS-acetylene (0.765 mL, 5.38 mmol) was dissolved in
THF (5.0 mL) and cooled to −60 °C. n-BuLi (2.15 mL, 2.5 M in n-
hexane, 5.38 mmol) was added and the solution was allowed
to stir for 30 minutes. This mixture was added dropwise to a
solution of HAB-benzophenone derivative 3 (495 mg,
0.538 mmol) in THF (100 mL). The colourless solution was
allowed to warm to room temperature and stirred for one day.
Afterwards it was hydrolysed with water (6.0 mL) and filtered.
The solvent was removed, the white solid was purified by
column chromatography (silica, CHCl3/n-hexane, 2:1. v/v)
(Rf = 0.37). The white solid was dried under vacuum. The
product was isolated in a yield of 86 % (437 mg, 462 µmol).
4
(CArH), 130.0 (CArH), 129.2 (CArH), 128.8 (t, JC,P = 5.0 Hz, m-
PPh3), 123.9 (CArH), 123.7 (2×CArH), 123.7 (2×CArH), 93.3 (CCp),
34.5 (2×C(CH3)3), 34.4 (C(CH3)3), 34.4 (2×C(CH3)3), 31.4
(2×C(CH3)3), 31.3 (3×C(CH3)3).
31P{1H} NMR (CD2Cl2 , 162 MHz):  [ppm]  46.7 (s, PPh3),
144.3 (sept, 2JP,F = 713 Hz, PF6).
HRMS (ESI/+MS/MeOH): m/z (%) = 1617.7030 (100) [M−PF6]+.
Calculated: 1617.7043.
EA: C112H109F6P3Ru (1763.09 gmol1): calcd [%]: C 76.30, H 6.23;
C112H109F6P3Ru × CH2Cl2 (1848.01gmol1): calcd: C 73.44, H
6.05; found: C 73.44, H 6.20 %.
IR (CH2Cl2):  [cm−1] = 2965 ( CalkylH, m), 2905( CalkylH, w),
2868 ( CalkylH, w), 1935 ( C=C=C, m), 1595 ( CAr=C, m),
1090 ( PC/  CArCAr, w).
1H NMR (CDCl3, 400 MHz, rt.):  [ppm]  7.34 (dd, JH,H = 1.7,
3
8.0 Hz, 2H, o-CArH), 7.26–7.24 (m, 3H, m/p-PhH), 7.10 (d,
3JH,H = 8.4 Hz, 2H, o-PhH), 6.84–6.80 (m, 12H, CArH), 6.71–
6.66 (m, 10 H, m-CArH), 2.72 (s, 1H, C≡CH), 2.58 (bs, 1H, OH),
1.12 (s, 18H, C(CH3)3), 1.11 (s, 27H, 3×C(CH3)3).
13C{1H} NMR (CDCl3, 151 MHz, rt.):  [ppm]  147.8 (CAr), 147.6
(CAr), 147.6 (CAr), 144.8 (CAr), 141.3 (CAr), 140.8 (CAr), 140.7
(CAr), 140.7 (CAr), 140.3 (CAr), 139.6 (CAr), 138.0 (CAr), 138.0
HBC-benzophenone derivative 6
(CAr), 137.9 (CArH), 131.6 (CArH), 131.3 (CArH), 131.2 (2×CArH), A round-bottom SCHLENK-flask (500 mL) equipped with a
128.2 (CArH),
123.3 (CArH),
127.7 (CAr),
123.2 (CArH),
126.2 (CArH),
123.2 (CArH),
124.5 (CArH), magnetic stirring bar was charged with HAB-benzophenone
86.6 (C≡CH), derivative 3 (0.600 g, 0.650 mmol) and CH2Cl2 (400 mL). The
75.2 (C≡CH), 74.2 (COH), 34.2 (C(CH3)3), 34.2 (C(CH3)3), solution was degassed with N2 for 40 min and meanwhile
31.4 (C(CH3)3), 31.3 (C(CH3)3). cooled to 0 °C in an ice bath. Dry FeCl3 (1.69 g, 10.4 mmol)
HRMS (ESI/+MS/MeOH): m/z (%) = 927.5880 (100) [M−OH]+, dissolved in MeNO2 (5.60 mL) was added portion wise. After
957.5804 (85) [M+Na]+, 983.5540 (50) [M+K]+. Calculated:
927.5863, 967.5788, 983.5528.
complete addition of the FeCl3 and solution degassing, cooling
was continued for 1 h. The ice-bath was removed, the N2
EA: C71H76O (945.39 gmol1) [%]: calcd: C 90.20, H 8.10; found: stream was stopped and the dark mixture was stirred for
C 90.11, H 8.08.
further 4 h at room temperature. The reaction was quenched
IR:  [cm1] = 3548 ( OH, w)3307 ( C≡CH, w), 3035 ( by addition of MeOH (150 mL). All solvents were evaporated
CArH, w), 2960 ( CalkylH, s), 2901 ( CalkylH, m), 2864 ( and the remaining solids were filtered over a plug of silica with
CalkylH, m), 1460 (CalkylH, m), 1393 ( CalkylH/  OH, m), CH2Cl2. The yellow product fraction was collected the solvents
1360( CalkylH/  OH, m), 1018 (out of plane CArH, s), 832 (out were concentrated and the product was precipitated from the
of plane CArH, s), 761 (out of plane CArH, m), 698 (out of plane CArH, CH2Cl2 solution by addition of MeOH. The yellow solid was
m).
filtered off, washed with a small amount of MeOH and dried
under vacuum. The product was obtained as a bright yellow
solid with a yield of 94 % (0.550 g, 0.610 mmol).
[Ru(5-C5H5)(=C=C=C(Ph)(HAB))(PPh3)2][PF6] (5)
The propargyl alcohol 4 (90.0 mg, 0.0952 mmol), [RuCl(5- 1H NMR (CDCl3, 400 MHz, rt.): δ [ppm] = 9.45 (s, 2H), 9.23 (s,
C5H5)(PPh3)2] (69.1 mg, 0.0952 mmol) and ammonium 2H), 9.22 (s, 2H), 9.19 (s, 2H), 9.17 (s, 2H), 9.05 (s, 2H), 8.18–
hexafluorophosphate (15.5 mg, 0.0952 mmol) were suspended 8.15 (m, 2H), 7.77–7.74 (m, 1H), 7.68–7.64 (m, 2H), 1.83 (s,
in MeOH (40.0 mL). The suspension was stirred at room 9H), 1.82 (s, 18H), 1.74 (s, 18H).
temperature for four days. Afterwards, the solvent was 13C{1H} NMR (CDCl3, 100 MHz, rt.): δ [ppm] = 197.3, 149. 2,
removed and the dark purple solid was purified by column 149.1, 149.0, 138.1, 134.4, 132.7, 130.7, 130.5, 130.4, 130.3,
chromatography (silica, CH2Cl2/acetone 11:1, v/v) (Rf = 0.5). 130.2, 130.1, 129.8, 128.4, 128.1, 123.7, 123.65, 123.57, 123.0,
6 | J. Name., 2012, 00, 1-3
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121.3, 121.1, 120.3, 119.28, 119.26, 118.93, 118.89, 35.75, 1H NMR (CDCl3, 600 MHz, rt.):  [ppm]  9.69 (s, 2H, CArH),
View Article Online
35.71, 35.69, 32.0, 31.9.
9.40–9.39 (two overlapping s, 4H, CArHD),O9I:.1307.1(0o3v9e/Drl0aDpTp0i2n7g29sD,
3
MS (MALDI-ToF, dhb): m/z = 907 [M]+.
4H, CArH), 9.17 (s, 2H, CArH), 7.87 (t, 1H, JH,H = 7.5 Hz, p-PhH),
HRMS (APPI, toluene): m/z = 906.48046 [M]+. Calculated: 7.69 (d, 2H, JH,H = 7.5 Hz, o-PhH), 7.55 (t, 2H, JH,H = 7.7 Hz, m-
3
3
906.47952.
PhH), 7.32 (t, 6H, 3JH,H = 7.0 Hz, p-PPh3H), 7.20–7.14 (m, 25H, o-
/m- PPh3H), 5.25 (s, 5H, CCpH), 1.87 (s, 9H, C(CH3)3), 1.86 (s,
18H, 2×C(CH3)3), 1.75 (s, 18H, 2×C(CH3)3).
13C{1H} NMR (CDCl3, 151 MHz, rt.):  [ppm]
 290.7 (t,
HBC-Phenylpropargyl alcohol 7
2JC,P = 18.1 Hz, C), 209.0 (C), 159.9 (C), 150.2 (CAr), 149.9 (d,
2JC,P = 7.0 Hz, i-PPh3), 144.7 (i-Ph), 141.3 (CAr), 135.4 (CAr), 135.3
(CAr), 135.0 (p-PPh3), 134.8 (CAr), 133.3 (t, 3JC,P = 5.0 Hz, o-PPh3),
132.1 (p-Ph), 131.9 (CAr), 131.0 (CAr), 130.9 (o-Ph), 130.8 (CAr),
130.4 (CAr), 129.8 (CAr), 129.3 (m-Ph), 129.0 (CAr), 128.7 (t,
4JC,P = 5.0 Hz, m-PPh3), 124.4 (CAr), 123.9 (CAr), 123.8 (CAr),
123.7 (CH), 122.4 (CAr), 121.6 (CAr), 121.1 (CAr), 120.3 (CArH),
120.0 (CAr), 119.6 (CArH), 119.4 (CArH), 119.3 (CArH),
119.3 (CArH), 93.9 (CCp), 36.0 (C(CH3)3), 36.0 (2×C(CH3)3), 32.2
(C(CH3)3), 32.1 (C(CH3)3), 32.1 (C(CH3)3).
TMS-acetylene (0.862 mL, 6.06 mmol) was dissolved in
THF (10 mL) and cooled to −60 °C. n-BuLi (2.42 mL, 2.5 M in n-
hexane, 6.06 mmol) was added and the solution was allowed
to stir for 1 h. This mixture was added dropwise to a solution
of HBC-benzophenone derivative 6 (550 mg, 0.606 mmol) in
THF (80 mL). The yellow solution was allowed to warm to room
temperature and stirred for 21 h. Afterwards, it was
hydrolysed with water (3 mL) and filtered. The solvent was
removed, the yellow solid was dissolved in CH2Cl2 (80 mL) and
washed with water (3 × 100 mL). The combined organic phases
were dried (Na2SO4). The solvent was removed and the yellow
solid dried under vacuum. The product was isolated in a yield
of 99 % (562 mg, 602 µmol)
31P{1H} NMR (CDCl3, 162 MHz):  [ppm] 46.1 (PPh3),
−144.2 (sept, 2JP,F = 713 Hz, PF6).
HRMS (ESI/+MS/MeOH): m/z (%) = 1605.6104 (96.0) [M−PF6]+.
Calculated: 1605.6135
1H NMR (CDCl3, 400 MHz, rt.):  [ppm]  9.41 (s, 2H, CHAr),
9.34 (3 partially overlapping s, 4H, CHAr), 9.31 (s, 2H, CHAr),
EA: C112H97F6P3Ru (1750.99 gmol1): calcd [%]: C 76.83, H 5.58;
found: C 77.23, H 5.82.
3
9.29 (s 2H, CHAr), 9.16 (s, 2H, CHAr), 7.92 (d, 2H, JH,H = 7.4 Hz,
IR (CH2Cl2):  [cm−1] = 2980 (CalkylH), 1927 (C=C=C),
1607 (CAr=C), 1591 (CAr=C), 1435 (PC).
3
3
o-PhH), 7.48 (t, 2H, JH,H = 7.6 Hz, m-PhH), 7.40 (t, 1H, JH,H
=
7.3 Hz, p-PhH), 3.31 (br, 1H, OH), 3.20 (s, 1H, C≡CH), 1.87 (s,
9H, C(CH3)3), 1.86 (s, 18 H, 2×C(CH3)3), 1.80 (s, 18H, 2×C(CH3)3).
13C{1H} NMR (CDCl3, 151 MHz, rt.):  [ppm]  149.3 (CAr), 149.2
(CAr), 144.7 (i-Ph), 142.0 (CAr), 142.0 (CAr), 131.0 (CAr), 131.0
(CAr), 130.7 (CAr), 130.6 (CAr), 130.5 (CAr), 130.5 (CAr), 130.2
(CAr), 128.7 (m-Ph), 128.3 (p-Ph), 126.7 (o-Ph), 125.5 (CAr),
124.1 (CAr), 124.0 (CAr), 121.0 (CAr), 120.9 (CAr), 120.6 (CAr),
120.2 (CAr), 119.7 (CH), 119.4 (CH), 119.3 (CH), 119.1 (CH),
119.1 (CH), 119.0 (CH), 87.1 (C≡CH), 76.3 (C≡CH), 75.4 (COH),
35.9 (C(CH3)3), 35.9 (C(CH3)3), 35.9 (C(CH3)3), 32.2 (C(CH3)3),
32.1 (C(CH3)3).
HRMS (ESI/+MS/MeOH): m/z (%) = 915.4902 (99) [M−OH]+,
932.4928 (100) [M]+, 955.4823 (22) [M+Na]+. Calculated:
915.4930, 932.4957, 955.4849.
EA: C71H64O (933.29 gmol1): calcd [%]: C 91.37, H 6.91; found:
C 89.95, H 7.04.
Conflicts of interest
There are no conflicts to declare.
Notes and references
‡ CCDC 2005956 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/structures.
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DOI: 10.1039/D0DT02729D
Hexa-peri-hexabenzocoronene decorated with an allenylidene ruthenium complex – almost a flyswatter
A ruthenium allenylidene complex bearing a hexa-peri-hexabenzocoronene (HBC) substituent was
synthesised, resembling yet another strategy to decorate HBCs with transition metal fragments.