Synthesis of the cyclohexadienyl ruthenium arene complexes [(η5-C6H3Me4)Ru(η6-arene)]+from the dimethyloctadienyl ruthenium chloride[(μ-η3:η3-C10H16)RuCl2]2

Article abstract of DOI:10.1016/j.jorganchem.2014.08.003

Reaction of the readily accessible dimethyloctadienyl ruthenium chloride [(μ-η³:η³-C₁₀H₁₆)RuCl₂]₂(1) with 1,3,5,5-tetramethylcyclohexadiene and arenes in the presence of TlPF₆gives cyclohexadienyl ruthenium arene complexes [(η⁵-C₆H₃Me₄)Ru(η⁶-arene)]⁺in ca. 50% yield (arene = benzene, naphthalene, pyrene, thiophene, ethyl ester of N-acetyl-phenylalanine). In the absence of appropriate arene the major product is the mesitylene complex [(η⁵-C₆H₃Me₄)Ru(η⁶-C₆H₃Me₃)]⁺formed via splitting of the C-Me bond in the 1,3,5,5-tetramethylcyclohexadienyl ligand. The reaction of 1 with p-xylene and TlPF₆in the absence of diene gives a methyl-isobutyl substituted pentadienyl complex [(η⁵-C₅H₅(ⁱBu)Me)Ru(η⁶-C₆H₄Me₂)]⁺(6) via isomerization of the dimethyloctadienyl ligand. The structures of [(η⁵-C₆H₃Me₄)Ru(η⁶-naphthalene)]PF₆and [6]BPh₄were confirmed by X-ray diffraction.

Full text of DOI:10.1016/j.jorganchem.2014.08.003

Journal of Organometallic Chemistry 770 (2014) 1e5
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis of the cyclohexadienyl ruthenium arene complexes
5
6
þ
3
[(h -C H Me )Ru(h -arene)] from the dimethyloctadienyl
6 3 4
3
ruthenium chloride[(m-h :h -C H )RuCl ]
10 16 2 2
Evgeniya A. Trifonova, Dmitry S. Perekalin, Natalia L. Loskutova, Yulia V. Nelyubina,
*
Alexander R. Kudinov
A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991 Moscow, Russian Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 4 July 2014
Received in revised form
Reaction of the readily accessible dimethyloctadienyl ruthenium chloride [(
m
-
h3
:
h3-C10H16)RuCl2]2 (1)
with 1,3,5,5-tetramethylcyclohexadiene and arenes in the presence of TlPF
6
gives cyclohexadienyl
5
6
þ
ruthenium arene complexes [(
h
-C
6
H
3
Me
4
)Ru(h
-arene)] in ca. 50% yield (arene ¼ benzene, naph-
30 July 2014
thalene, pyrene, thiophene, ethyl ester of N-acetyl-phenylalanine). In the absence of appropriate arene
the major product is the mesitylene complex [(
Accepted 1 August 2014
Available online 11 August 2014
5
6
þ
3
6 3 4 6 3
h -C H Me )Ru(h -C H Me )] formed via splitting of
the CeMe bond in the 1,3,5,5-tetramethylcyclohexadienyl ligand. The reaction of 1 with p-xylene and
5
i
TlPF
Me)Ru(
Me
6
in the absence of diene gives a methyl-isobutyl substituted pentadienyl complex [(
h
-C
5
H
5
( Bu)
Keywords:
6
þ
5
h
-C
6
4
H Me
6
2
)] (6) via isomerization of the dimethyloctadienyl ligand. The structures of [(
and [6]BPh were confirmed by X-ray diffraction.
© 2014 Elsevier B.V. All rights reserved.
h
-
Arene ligands
Cyclohexadienyl
Ruthenium
C
6
H
3
4
)Ru(h
-naphthalene)]PF
6
4
Sandwich complexes
Introduction
is air-sensitive even in the solid state and its three-step synthesis is
5
somewhat complicated [9]. In addition, reactions of [(
Ru(MeCN) ]
3
h
-C
þ
are often accompanied by hydrogen abstraction
6 7
H )
Cyclopentadienyl ruthenium arene complexes [CpRu(h6-are-
þ
ne)] are used in many areas of organometallic chemistry owing to
which converts cyclohexadienyl ligand into benzene. In order to
avoid this side process it is desirable to use 6,6-disubstituted
cyclohexadienyl ligands. Herein we report a simple synthesis of
simplicity of their synthesis and high chemical stability [1]. In
particular, such compounds were employed for activation of
nucleophilic substitution in arenes [2], for modification of ligands
5
6
3
such substituted cyclohexadienyl complexes [(
h
-C
6
H
3
Me
4
)Ru(
h
-
-
þ
3
[3] and biomolecules [4], as well as in homogeneous catalysis [5]
arene)] from the air-stable easily accessible precursor [(
m
-h
:h
and anti-cancer studies [6].
10 2 2
C H16)RuCl ] (1).
Although analogous cyclohexadienyl complexes [(h5-C
6 7
H )
Ru( 6
h -arene)] can find similar application, their chemistry is
þ
notably less developed. This is partially explained by a more
Results and discussion
complicated synthesis of such complexes. Usually they are obtained
3 2
Cox and Roulet have reported that heating RuCl $xH O with
6
by nucleophilic addition of a hydride to the dications [(
h
-C
6
H
6
)
isoprene gives the air-stable chloride complex 1 (Scheme 2) [10].
This compound proved to be a useful precursor for various ruthe-
nium complexes [11]. In particular, Salzer et al. have noted that 1
reacts with 2,4-dimethylpentadiene and benzene in the presence of
6
2þ
Ru(h
-arene)]
(Scheme 1) [7]. However, this reaction is not
compatible with many functional groups and may be complicated
by further reduction giving neutral cyclohexadiene derivatives.
We have recently developed an alternative approach to the
5
6
AgBF
4
giving the cationic dienyl complex [(
h
-C
5 5 2
H Me )Ru(h -
5
6
þ
cyclohexadienyl complexes [(
h
-C H
6 7
)Ru(h
-arene)] based on
þ
C
6
H
6
)] (2) [12]. In the present work we extended this method
5
replacement of the labile acetonitrile ligands in [(
h
-C H
6 7
)
using 1,3,5,5-tetramethylcyclohexadiene (3), which is easily syn-
thesized in one step from the commercially available isophorone
and MeLi [13].
þ
Ru(MeCN)
3
]
by arenes [8]. Unfortunately, the acetonitrile complex
It was found that chloride 1 reacts with diene 3 and benzene in
the presence of TlPF
cyclohexadienyl complex [(
6
(as a chloride-abstracting agent) giving the
*
Corresponding author.
E-mail address: arkudinov@ineos.ac.ru (A.R. Kudinov).
5
6
þ
6
6 3 4 6
h -C H Me )Ru(h -C H )] (4a) in 57%
http://dx.doi.org/10.1016/j.jorganchem.2014.08.003
022-328X/© 2014 Elsevier B.V. All rights reserved.
0

2
E.A. Trifonova et al. / Journal of Organometallic Chemistry 770 (2014) 1e5
bond and formation of 4f. Accordingly, the reaction of 1 with 3 and
TlPF in the absence of arenes gives the pure mesitylene complex 4f
6
in 53% yield. Several examples of similar CeC bond cleavage in
ruthenium cyclohexadienyl complexes have been reported previ-
ously [8b,16].
Interestingly, the reaction of chloride 1 with p-xylene and TlPF
6
5
6
in the absence of diene 3 gives complex [(
h -C10H17)Ru(h -
þ
C
6
H
4
Me
2
)] (6) in 41% yield (Scheme 5). Apparently, the methyl-
isobutyl-substituted pentadienyl ligand is formed by isomeriza-
tion of the dimethyloctadienyl ligand. Noteworthy, isobutyl sub-
stituent in 6 is in cis-position to the pentadienyl ligand despite of
the steric repulsion. The DFT calculations show that the hypothet-
Scheme 1.
ꢁ1
ical trans-isomer 7 is 3.4 kcal mol more stable than 6.
All the compounds obtained were characterized by H and 13C
NMR. Notably, the signals of the seemingly equivalent aromatic
protons of p-xylene in complex 6 appear as two doublets due to
1
chirality of the pentadienyl ligand. The structures of [4b]PF
6
and [6]
BPh were established by X-ray diffraction (Figs. 1 and 2). As ex-
4
pected the ruthenium atom in cation 4b is shifted away from the
bridgehead atoms of the naphthalene ligand so that RueC1 and
RueC6 bonds (av. 2.310 Å) are longer that other RueCnaphthalene
bonds (av. 2.227 Å). These values are close to those observed in
Scheme 2.
other ruthenium naphthalene complexes, particularly [(C
5
R
5
)
þ
Ru(C10
H
8
)] [6b,17]. The coordinated part of the cyclohexadienyl
yield (Scheme 3). Variations of the solvent (CH
as gradual addition of TlPF or diene did not significantly improve
the yield. An attempt to replace TlPF by cheaper and non-toxic
KPF results in no reaction, while the use of AgBF leads to un-
2 2
Cl , acetone) as well
ꢀ
ligand in 4b is almost planar and parallel (2.0 ) to the naphthalene
ligand. On the contrary, the pentadienyl ligand in cation 6 is
6
6
significantly non-planar (mean deviation from coordinated C
plane is 0.033 Å) and tilted by 11.2 relative to p-xylene plane.
Reasons for this distortion are not clear.
5
6
4
ꢀ
wanted redox processes. Similar reaction of 1 with 3 and other
arenes gives complexes 4bee in ca. 50% yield. Interestingly, poly-
cyclic arenes (naphthalene and pyrene) and thiophene react at
ꢀ
Conclusion
room temperature, while mild heating (60 C) is required for
benzene. The reaction is compatible with amide and ester func-
tional groups as exemplified by the synthesis of complex 4e with
phenylalanine derivative.
Overall, we have developed a new simple method for the syn-
thesis of cyclohexadienyl ruthenium arene complexes starting from
the readily available chloride [(m-h :h -C10H16)RuCl ] . The method
2 2
works well for polycyclic and functionalized arenes but is unsuit-
able for sterically-hindered or electron poor arenes.
3
3
On the other hand, reactions of chloride 1 with diene 3 and
poorly coordinating arenes are complicated by formation of the
5
6
þ
mesitylene complex [(
). In particular, the reaction with sterically-hindered durene
gives a mixture of the mesitylene (4f) and durene (4g) complexes in
:1 ratio. Similar reaction with electron poor chlorobenzene pro-
h -C H Me )Ru(h -C H Me )] (4f; Scheme
6 3 4 6 3 3
4
Experimental section
7
General
duces complexes 4f and 4h in 2:1 ratio [14]. We assume that in the
presence of poorly coordinating arene the reaction of 1 with 3
5
All reactions were carried out under argon atmosphere using
standard Schlenk techniques. Isolation of products was conducted
in air. Anhydrous solvents were purified and dried using standard
initially gives the bis(cyclohexadienyl) sandwich complex Ru(
h
-
C
H
6 3
Me (5). Indeed 5 was isolated if K CO
4
)
2
2
3
was added to the
reaction mixture in order to quench the acid [15]. In the presence of
acid, protonation of 5 occurs resulting in a cleavage of the СeMe
procedures. The NMR spectra were measured with Bruker Avance
ꢀ
4
00 spectrometer at 25 C in acetone-d
6
unless otherwise stated.
Chemical shifts are given in ppm relative to the residual signal of
the solvents. Compound 1 was prepared according to literature
procedures [10,12] by heating RuCl
3
$xH
2
O with isoprene and
ꢀ
2-methoxyethanol at 60 C in a closed glass vessel.
Synthesis of 1,3,5,5-tetramethylcyclohexadiene (3)
This compound was obtained by variation of the literature
procedures [18,19]. Isophorone (30 ml, 0.20 mol) was added
ꢀ
dropwise to an ethereal solution of MeLi (150 ml, 0.24 mol) at 0 C.
After the addition, the reaction mixture was stirred for 2 h at room
temperature, and then quenched with saturated aqueous NH Cl.
4
The water layer was neutralized by aqueous HCl and the ether layer
was separated. The water layer was extracted with additional
1
00 ml of ether, the organic fractions were combined, washed with
aqueous NaHCO and dried over Na SO . The resulting ether solu-
tion was treated with TsOH$H O (1.5 g, 7.89 mmol) and stirred
overnight at room temperature. The mixture was neutralized with
3
2
4
2
Scheme 3.

E.A. Trifonova et al. / Journal of Organometallic Chemistry 770 (2014) 1e5
3
Scheme 4.
aqueous NaHCO
3
. The ether layer was separated, dried over Na
2
SO
4
6
Then solid TlPF (147 mg, 0.42 mmol) was added in 6 portions
and carefully evaporated to a volume of ca. 50 ml. The residue was
distilled in vacuum (50 C at 12 torr) to give a mixture of 1,5,5-
during 30 min under vigorous stirring. The reaction mixture was
heated at 60 C for 6 h and then evaporated to dryness. The residue
ꢀ
ꢀ
trimethyl-3-methylenecyclohex-1-ene
and
1,3,5,5-
was dissolved in CH
(4 ꢂ 1 cm) with CH
2
Cl
2
and eluted through a short alumina column
2
/acetone mixture (1:1). The resulting solu-
tetramethylcyclohexa-1,3-diene in ca. ratio 1:1, respectively. Total
yield is 22 ml (0.13 mol, 65%). The mixture of dienes was further
used without separation.
2
Cl
tion was evaporated to dryness, the solid was reprecipitated from
CH Cl /Et O and washed with Et
O (3 ꢂ 5 ml) to give white crys-
talline [4a]PF (52 mg, 0.11 mmol, 57% yield).
H NMR (400 MHz): Me
¼ 6.62 (s, 1H, C
3.71 (s, 2H, C Me ), 1.99 (s, 6H, CH ), 1.31 (s, 3H, CH
). C NMR (101 MHz): Me
¼ 102.27 (1C, C
), 88.84 (2C, C Me ), 54.26 (2C, C Me ), 37.18 (2C, CH
32.97 (1C, CH ), 20.53 (1C, CH ). Anal. Calc. for C16 PRu: C,
41.83; H, 4.61. Found: C 41.96; H, 4.50.
2
2
2
2
1
,5,5-trimethyl-3-methylenecyclohex-1-ene:
400 MHz, CDCl ):
¼ 5.98e5.92 (m, 1H, CH), 4.75 (d, J ¼ 0.5 Hz,1H,
CH ), 2.05 (s, 2H, CH ), 1.86 (s, 2H, CH ),
), 4.68 (d, J ¼ 0.5 Hz, 1H, CH
.76 (s, 3H, CH ), 0.93 (s, 6H, CH ). Cf. [19].
,3,5,5-tetramethylcyclohexa-1,3-diene: 1H NMR (400 MHz,
CDCl ): ),
¼ 5.57e5.48 (m, 1H, CH), 5.08 (s, 1H, CH), 1.94 (s, 2H, CH
.79 (s, 3H, CH ), 0.97 (s, 6H, CH ). Cf. [19].
),1.72 (d, J ¼ 1.4 Hz, 3H, CH
1H
NMR
6
1
(
3
d
d
6
H
3
4
), 6.36 (s, 6H, C
), 0.41 (s, 3H,
), 90.62 (6C,
),
6 6
H ),
2
2
2
2
6
H
3
4
3
3
13
1
3
3
CH
3
d
6
H
3
4
1
C
6
H
6
6
H
3
4
6
H
3
4
3
3
d
2
3
3
21 6
H F
1
3
3
3
Synthesis of [4a]PF
6
Diene 3 (0.14 ml, 0.8 mmol) and benzene (0.35 ml, 4 mmol) were
added to a suspension of 1 (62 mg, 0.1 mmol) in ethanol (3 ml).
Fig. 1. The structure of cation 4b in 50% thermal ellipsoids. All hydrogen atoms are
omitted for clarity. Selected interatomic distances (Å): Ru1eC1 2.311(6), Ru1eC2
2
.202(5), Ru1eC3 2.264(6), Ru1eC4 2.247(6), Ru1eC5 2.196(6), Ru1eC6 2.308(6),
Ru1eC11 2.207(6), Ru1eC12 2.188(6), Ru1eC13 2.178(6), Ru1eC14 2.192(6), Ru1eC15
2.193(6), Ru/C (plane) 1.693, Ru/C (plane) 1.754.
Scheme 5.
5
6

4
E.A. Trifonova et al. / Journal of Organometallic Chemistry 770 (2014) 1e5
8
7.96, 87.49, 55.72 (2C, C
CH ), 27.96 (1C, CH ), 18.44 (1C, CH
3.52; H, 4.32. Found: C, 53.41; H, 4.17.
6
H
3
Me
4
), 37.49 (1C, C ), 32.51 (2C,
6
H
3
Me
4
3
3
3
). Anal. Calc. for C26H F PRu: C,
25 6
5
Synthesis of [4d]PF
6
The yellow crystalline compound [4d]PF
8% yield) was isolated as described for [4b]PF
6
(45 mg, 0.10 mmol,
using thiophene
4
6
instead of naphthalene.
1
H NMR (400 MHz):
d
¼ 6.37 (s, 1H, C
6
H
3
Me
4
), 6.35 (dd, J ¼ 2.3,
S), 3.84 (s, 2H,
1
C
.6 Hz, 2H, C
Me ), 1.95 (s, 6H, CH
NMR (101 MHz):
¼ 103.76 (1C, C
9.91 (2C, C Me ), 38.43 (1C, C
1C, CH ), 21.15 (1C, CH ). Anal. Calc. for C14
.11. Found: C, 36.13; H, 4.15.
4
H
4
S), 6.17 (dd, J ¼ 2.3, 1.6 Hz, 2H, C
), 1.44 (s, 3H, CH ), 0.52 (s, 3H, CH
Me ), 92.69, 87.85, 80.99,
Me ), 33.55 (2C, CH ), 29.82
PRuS: C, 36.13; H,
4 4
H
13
6
H
3
4
3
3
3
).
C
d
6
H
3
4
5
(
4
6
H
3
4
6
H
3
4
3
3
3
19 6
H F
Synthesis of [4e]BPh
4
Synthesis of [4e]PF
6
was performed as described for [4a]PF
6
using N-acetyl phenylalanine ethyl ester (235 mg, 1.0 mmol)
instead of benzene. The reaction mixture was evaporated, the res-
idue was dissolved in acetone and an excess of solid NaBPh
137 mg, 0.4 mmol) was added. The mixture was stirred for 1 h to
ensure counter-ion exchange and then evaporated. The residue was
dissolved in CH Cl and filtered. The solution was evaporated, the
residue was washed with water, Et O and dried in vacuum to give
as colorless oily solid (60 mg, 0.10 mmol, 49% yield).
H NMR (400 MHz):
¼ 7.52 (d, J ¼ 7.0 Hz, 1H, NH), 6.56 (s, 1H,
Me ), 6.39e6.22 (m, 5H, Ph), 4.72 (m, 1H, NeCH), 4.15 (q,
), 3.61 (s, 2H, C Me
), 3.05 (dd, J ¼ 13.0, 5.0 Hz,
), 2.91 (m, 1H, CH ), 1.96 (s, 6H, CH ), 1.89 (s, 3H, CH ), 1.29
s, 3H, CH ), 0.40 (s, 3H, CH
), 1.21 (t, J ¼ 7.0 Hz, 3H, CH
101 MHz):
¼ 170.30, 169.25, 164.80 (q, JBC ¼ 49.5 Hz, 4C, BPh
4
Fig. 2. The structure of cation 6 in 50% thermal ellipsoids. All hydrogen atoms except
those at C1 and C5 atoms are omitted for clarity. Selected interatomic distances (Å):
Ru1eC1 2.151(6), Ru1eC2 2.183(6), Ru1eC3 2.212(5), Ru1eC4 2.150(6), Ru1eC5
(
2.224(6), Ru1eC11 2.290(8), Ru1eC12 2.255(7), Ru1eC13 2.226(7), Ru1eC14 2.246(7),
2
2
Ru1eC15 2.219(7), Ru1eC16 2.222(7), Ru/C (plane) 1.743.
6
2
[4e]BPh
4
1
d
Synthesis of [4b]PF
6
C
3
H
3
4
J ¼ 7.0 Hz, 2H, CH
2
3
H
3
4
Diene 3 (0.136 ml, 0.8 mmol) was added to a suspension of 1
1
(
(
H, CH
2
2
3
3
(
(
62 mg, 0.1 mmol) and naphthalene (256 mg, 2 mmol) in ethanol
13
3
3
3
). C NMR
),
4
), 121.41 (s, 4C,
3 ml) and CH
(147 mg, 0.42 mmol) was added in 6 portions during
0 min under vigorous stirring. The reaction mixture was stirred
overnight at room temperature and then evaporated to dryness.
2
Cl
2
(1 ml, improves solubility of reactants). Then
1
d
4
solid TlPF
3
6
3
1
36.18 (s, 8C, BPh
4
), 125.16 (q, JBC ¼ 2.8 Hz, 8C, BPh
), 105.55, 102.28, 91.26, 90.18, 90.12, 88.67, 61.23 (OCH
), 21.79 (CH ), 20.46 (CH
BPh
4
2
CH
3
),
),
54.58, 53.18, 37.29, 36.01, 33.01 (CH
3
3
3
The residue was dissolved in CH
alumina column (4 ꢂ 1 cm) with CH
2
Cl
2
and eluted through a short
/acetone mixture (1:1). The
1
3.56 (CH ). Anal. Calc. for C47 52BNO
3
H
3
Ru: C, 71.38; H, 6.63. Found:
2
Cl
2
C, 71.64; H, 6.78.
resulting yellow solution was evaporated to dryness, the solid was
reprecipitated from CH Cl /Et O and washed with Et
O (3 ꢂ 5 ml)
to give yellow crystalline [4b]PF (56 mg, 0.11 mmol, 55% yield).
Crystals for X-ray study were grown by slow diffusion of Et O va-
pors into solution of complex in CH Cl
¼ 7.94 (dd, J ¼ 7.0, 3.0 Hz, 2H, C10
), 6.97 (dd, J ¼ 5.0, 3.0 Hz, 2H, C10
.61 (dd, J ¼ 5.0, 3.0 Hz, 2H, C10 ), 6.05 (s, 1H, C Me ), 3.40 (s,
H, C Me ), 1.74 (s, 6H, CH ), 0.92 (s, 3H, CH ), 0.24 (s, 3H, CH
C NMR (101 MHz): ), 128.71 (2C, C10
¼ 131.98 (2C, C10
Me
), 19.51 (1C, CH
O: C, 48.35; H, 5.16. Found: C, 48.67;
2
2
2
2
Synthesis of [4f]BF
4
6
2
Diene 3 (0.136 ml, 0.8 mmol) was added to a suspension of 1
2
2
.
(62 mg, 0.1 mmol) and TlBF
4
(145 mg, 0.5 mmol) in ethanol (3 ml).
1
H NMR (400 MHz):
d
H
8
), 7.85
),
ꢀ
The reaction mixture was heated at 60 C for 6 h and then evapo-
(
dd, J ¼ 7.0, 3.0 Hz, 2H, C10
H
8
H
8
rated to dryness. The residue was treated as in the case of [4a]PF
afford white crystalline [4f]BF (46 mg, 0.10 mmol, 52% yield).
Alternatively to solution of bis(2,4,6,6-
tetramethylcyclohexadienyl)ruthenium (5) (46 mg, 0.12 mmol) in
ether (3 ml) HBF $Et O (0.025 ml, 0.19 mmol) was added. The re-
action mixture was stirred for 1 h at room temperature, then the
ether was decanted and solid residue was washed with Et
6
to
6
2
H
8
6
H
3
4
4
6
H
3
4
3
3
3
8
).
),
a
1
3
d
H
8
H
1
C
01.99, 100.79, 91.40, 87.46, 87.21, 54.79 (2C, C
6
H
3
4
), 38.06 (1C,
). Anal.
4
2
6
H
3
Me
4
), 33.05 (2C, CH
3
), 27.37 (1C, CH
3
3
Calc. for C20
H, 5,15.
H
23
F
6
PRu ꢂ 0.5Et
2
2
O
(
(
3 ꢂ 3 ml). Reprecipitation from CH
2 2 2 4
Cl /Et O gives pure [4f]BF
36 mg, 0.08 mmol, 68% yield).
1
Synthesis of [4c]PF
6
H NMR (400 MHz):
Me ), 3.22 (s, 2H, C
), 0.40 (s, 3H, CH
102.16, 90.93, 87.58, 55.44 (2C, C
CH ), 20.29 (1C, CH ), 18.73 (1C, CH
51.48; H, 6.14. Found: C 51.46; H, 6.17.
d
¼ 6.33 (s, 1H, C
6
H
3
Me
), 1.99 (s, 6H, CH
). C NMR (101 MHz):
¼ 106.02,
Me ), 37.28 (2C, CH ), 32.84 (3C,
). Anal. Calc. for C19 Ru: C,
4
), 6.11 (s, 3H,
C
6
H
3
3
6
H
3
Me ), 2.37 (s, 9H, CH
4
3
3
),
13
The yellow crystalline compound [4c]PF
6% yield) was isolated as described for [4b]PF
6
(53 mg, 0.09 mmol,
using pyrene
1.32 (s, 3H, CH
3
3
d
4
6
6
H
3
4
3
instead of naphthalene.
3
3
3
H27BF
4
1
H NMR (400 MHz):
d
¼ 8.37 (dd, J ¼ 11.0, 9.0 Hz, 4H, C14
10), 7.94 (d, J ¼ 9.0 Hz, 2H, C14 10), 7.27e7.18
10), 5.30 (s, 1H, C Me ), 3.18 (s, 2H, C Me ), 1.27 (s,
), 1.17 (s, 3H, CH ), 0.10 (s, 3H, CH ). C NMR (101 MHz):
¼ 133.06 (C14 10), 131.68 (C14 10), 129.80 (C14 10), 128.94
10), 127.35 (C14 10), 125.15 (C14 10), 98.99, 97.59, 96.02, 90.89,
H10),
8
(
6
d
.30e8.24 (m, 1H, C14
m, 3H, C14
H, CH
H
H
H
H
6 3
4
6
H
3
4
Synthesis of [6]PF
6
13
3
3
3
H
H
H
H
To a suspension of 1 (62 mg, 0.1 mmol) in ethanol (3 ml) and p-
xylene (0.5 ml, 4 mmol) solid TlPF (147 mg, 0.42 mmol) was added
(
C
14
H
H
6

E.A. Trifonova et al. / Journal of Organometallic Chemistry 770 (2014) 1e5
5
in 6 portions during 30 min under vigorous stirring. The reaction
Appendix A. Supplementary material
ꢀ
mixture was heated at 60 C for 10 h and then evaporated to dry-
ness. The residue was dissolved in CH Cl and eluted through a
short alumina column (4 ꢂ 1 cm) with CH Cl /acetone mixture
1:1). The resulting solution was evaporated to dryness, the solid
was reprecipitated from CH Cl /Et O and washed with Et
3 ꢂ 5 ml) to give white crystalline [6]PF (40 mg, 0.08 mmol, 41%
yield).
In order to exchange the counter-anion for crystal growing the
compound [6]PF was dissolved in acetone and aqueous solution of
NaBPh (342 mg, 1.0 mmol) was added. The mixture was extracted
twice with CH Cl and the organic fraction was then dried over
Na SO . The solvent was evaporated and the residue was repreci-
pitated from CH Cl /Et O to give [6]BPh . Crystals for X-ray study
O vapors into solution of
2
2
CCDC 1010945 and 1010946 contain the supplementary crys-
tallographic 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.
2
2
(
2
2
2
2
O
(
6
Appendix B. Supplementary data
6
4
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jorganchem.2014.08.003.
2
2
2
4
2
2
2
4
were grown by slow diffusion of Et
2
References
complex in acetone.
1
H NMR (400 MHz):
d
¼ 6.39 (d, J ¼ 6.5 Hz, 1H, C10
), 6.26 (d, J ¼ 6.2 Hz, 2H, C Me
17), 3.87 (td, J ¼ 9.3, 4.0 Hz, 1H, C10
Me ), 2.15 (s, 3H, C10
17), 1.59 (dtd, J ¼ 8.2, 6.5, 4.0 Hz, 1H,
17),1.19 (dt, J ¼ 12.9, 4.0 Hz,1H, C10 17), 0.85 (dd, J ¼ 6.5, 4.0 Hz,
H, C10
17), 0.22 (dt, J ¼ 12.9, 9.3 Hz, 1H, C10
¼ 107.84, 106.26, 100.48, 92.54, 92.32, 84.80, 60.88,
9.07, 41.26, 29.83, 25.21, 22.26, 20.79, 18.02. Anal. Calc. for
47BRu: C, 76.01; H, 7.14. Found: C, 76.03; H, 7.18.
H
17), 6.30 (d,
), 5.07 (dd,
17), 3.47
17),
[1] (a) R.M. Moriarty, Y.-Y. Ku, U.S. Gill, J. Organomet. Chem. 362 (1989) 187;
J ¼ 6.2 Hz, 2H, C
6
4
H Me
2
6
H
4
2
(b) E.P. Kündig, Top. Organomet. Chem. 7 (2004) 3;
J ¼ 8.2, 6.5 Hz, 1H, C10
H
H
(c) D.S. Perekalin, A.R. Kudinov, Coord. Chem. Rev. 276 (2014) 153.
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G. Bernardinelli, E.P. Kündig, Chem. Eur. J. 16 (2010) 6285;
[
[
(
d, J ¼ 3.2 Hz, 1H, C10
H17), 2.35 (s, 6H, C
6
H
4
2
H
1
C
6
(
4
C
.67 (d, J ¼ 3.2 Hz, 1H, C10
H
10
H
H
(b) K. Verlinden, C. Ganter, J. Organomet. Chem. 750 (2013) 23;
13
ꢀ
ꢀ
H
H
17). C NMR
(c) N.A. Espinosa-Jalapa, S. Hernandez-Ortega, X.-F. Le Goff, D. Morales-Mo-
rales, J.-P. Djukic, R. Le Lagadec, Organometallics 32 (2013) 2661.
101 MHz): d
[4] D.S. Perekalin, E.E. Karslyan, P.V. Petrovskii, Y.V. Nelyubina, K.A. Lyssenko,
A.S. Kononikhin, E.N. Nikolaev, A.R. Kudinov, Chem. Eur. J. 16 (2010) 8466.
42
H
[5] (a) L. Hintermann, L. Xiao, A. Labonne, U. Englert, Organometallics 28 (2009)
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c) D.S. Perekalin, E.E. Karslyan, E.A. Trifonova, A.I. Konovalov, N.L. Loskutova,
5
(
3
(
DFT calculations
Y.V. Nelyubina, A.R. Kudinov, Eur. J. Inorg. Chem. (2013) 481.
Geometry optimizations were performed without constraints
using PBE exchange-correlation functional [20], the scalar-
relativistic Hamiltonian [21], atomic basis sets of generally-
contracted Gaussian functions [22], and a density-fitting tech-
nique [23] as implemented in Priroda 6 code [24]. The all-electron
[
6] (a) M.H. Garcia, A. Valente, P. Florindo, T.S. Morais, M.F. Piedade, M.T. Duarte,
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(
c) D.S. Perekalin, A.P. Molotkov, Y.V. Nelyubina, N.Y. Anisimova, A.R. Kudinov,
Inorg. Chim. Acta 409 (2014) 390.
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triple-z basis set L2 augmented by two polarization function was
(
(
(
1982) 215;
used [25]. Frequency calculations were performed to confirm the
nature of the stationary points. The ChemCraft software was used
for molecular modeling and visualization [26]. Cartesian co-
ordinates for optimized structures are available as Supplementary
Material to this article.
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[
[
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(b) See also: P.T. Dimauro, P.T. Wolczanski Polyhedron 14 (1995) 149.
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Mendeleev Commun. 23 (2013) 133.
X-ray crystallography
X-ray diffraction experiments for [4b]PF
carried out with a Bruker APEX2 DUO diffractometer using graphite
monochromated Mo-K radiation ( -scans) at 120 K.
6 4
and [6]BPh were
[
10] D.N. Cox, R. Roulet, Inorg. Chem. 29 (1990) 1360.
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3 2
14] Similar СeMe cleavage also occurs in the direct reaction of RuCl $xH O with
(
a
l
¼ 0.71073 Å,
u
[
The structures were solved by direct method and refined by the
full-matrix least-squares against F in anisotropic approximation
(
2
[
for non-hydrogen atoms. H(C) atom positions were calculated, and
they were refined in isotropic approximation in riding model. For
diene 3 and naphthalene which gives a mixture of the mesitylene complex 4f
and the naphthalene complex 4b in 2:3 ratio.
[
4b]PF
for all the independent reflections (R1 ¼ 0.0732 was calculated
against F for 4520 observed reflections with I > 2 (I)). For [6]BPh
6
the refinement converged to wR2 ¼ 0.1877 and GOF ¼ 1.234
[15] R.U. Kirss, Inorg. Chim. Acta 357 (2004) 3181.
16] (a) D. Rondon, B. Chaudret, X.-D. He, D. Labroue, J. Am. Chem. Soc. 113 (1991)
671;
b) F. Urbanos, M.A. Halcrow, J. Fernandez-Baeza, F. Dahan, D. Labroue,
B. Chaudret, J. Am. Chem. Soc. 115 (1993) 3484.
[
5
(
s
4
the refinement converged to wR2 ¼ 0.1082 and GOF ¼ 1.005 for all
the independent reflections (R1 ¼ 0.0555 was calculated against F
[17] E.E. Karslyan, D.S. Perekalin, P.V. Petrovskii, K.A. Lyssenko, A.R. Kudinov, Russ.
Chem. Bull. 57 (2008) 2201.
for 6410 observed reflections with I > 2s(I)). All calculations were
[18] O.H. Wheeler, J. Org. Chem. 20 (1955) 1672.
performed using the SHELXTL PLUS 5.0 software [27].
[19] P.C. Traas, H. Boelens, H.J. Takken, Recl. Trav. Chim. Pays Bas 95 (1976) 57.
[
[
[
[
20] J.P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 177 (1996) 3865e3868.
21] K.G. Dyall, J. Chem. Phys. 100 (1994) 2118.
22] D.N. Laikov, Chem. Phys. Lett. 416 (2005) 116e120.
23] D.N. Laikov, Chem. Phys. Lett. 281 (1997) 151e156.
Acknowledgments
The work was supported by the Russian Foundation for Basic
Research (grant # 14-03-32044) and by the Council of the President
[24] D.N. Laikov, Yu. A. Ustynyuk, Russ. Chem. Bull. 54 (2005) 820e826.
[25] E.Ya. Misochko, A.V. Akimov, V.A. Belov, D.A. Tyurin, D.N. Laikov, J. Chem.
Phys. 127 (2007) 084301.
of the Russian Federation (grant for young scientist #
261.2014.3).
МК-
[26] G.A. Zhurko, ChemCraft 1.6, http://www.chemcraftprog.com.
4
[27] G.M. Sheldrick, Acta Crystallogr. A 64 (2008) 112.