Reactions of the cyclopentadienyl ruthenium complexes (C5R 5)Ru(cod)Cl and [(C5R5)Ru(MeCN) 3]+ (R = H, Me) with phenylacetylene and acetic acid: Unexpected difference in reactivity of CpRu and Cp*Ru complexes

Article abstract of DOI:10.1016/j.jorganchem.2013.03.043

Reaction of CpRu(cod)Cl with phenylacetylene and AcOH gives an unusual binuclear ruthenium complex CpRu(μ-σ,η³: η³,σ-C₆H₃Ph₃)RuCp (5, 58% yield) with a bridging acyclic flyover ligand C₆H₃Ph ₃. Under similar conditions [CpRu(MeCN)₃]⁺ undergoes an unexpected cleavage of Cp ligand giving 4,7-diphenyl-3a,7a- dihydroindene (6, 65% yield). In sharp contrast, the pentamethylated congeners Cp*Ru(cod)Cl and [Cp*Ru(MeCN)₃]⁺ react with phenylacetylene and AcOH in catalytic fashion giving 1,4-diphenyl-1-acetoxy-1,3- butadiene. The structures of 5 and 6 were established by X-ray diffraction. The mechanism of Cp ligand cleavage was proposed on the basis of DFT calculations.

Full text of DOI:10.1016/j.jorganchem.2013.03.043

Journal of Organometallic Chemistry 737 (2013) 21e25
Contents lists available at SciVerse ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Reactions of the cyclopentadienyl ruthenium complexes (C5R5)Ru(cod)Cl and
[(C5R5)Ru(MeCN)3]þ (R ¼ H, Me) with phenylacetylene and acetic acid:
Unexpected difference in reactivity of CpRu and Cp*Ru complexes
Dmitry S. Perekalin, Evgeniya A. Trifonova, Valentin V. Novikov, Yulia V. Nelyubina,
*
Alexander R. Kudinov
A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova str. 28, 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:
Reaction of CpRu(cod)Cl with phenylacetylene and AcOH gives an unusual binuclear ruthenium complex
CpRu(m-s, : ,s-C6H3Ph3)RuCp (5, 58% yield) with a bridging acyclic flyover ligand C6H3Ph3. Under
h3 h3
Received 8 February 2013
Received in revised form
26 March 2013
similar conditions [CpRu(MeCN)3]þ undergoes an unexpected cleavage of Cp ligand giving 4,7-diphenyl-
3a,7a-dihydroindene (6, 65% yield). In sharp contrast, the pentamethylated congeners Cp*Ru(cod)Cl and
[Cp*Ru(MeCN)3]þ react with phenylacetylene and AcOH in catalytic fashion giving 1,4-diphenyl-1-
acetoxy-1,3-butadiene. The structures of 5 and 6 were established by X-ray diffraction. The mecha-
nism of Cp ligand cleavage was proposed on the basis of DFT calculations.
Accepted 28 March 2013
Keywords:
Ruthenium
Cyclopentadienyl
Catalysis
Ó 2013 Elsevier B.V. All rights reserved.
Alkynes
Bridging ligand
Flyover ligand
1. Introduction
2. Results and discussion
Cyclopentadienyl ruthenium complexes (C5R5)Ru(cod)Cl (R ¼ H
(1a), Me (1b), cod ¼ 1,5-cyclooctadiene; Chart 1) and [(C5R5)
Ru(MeCN)3]þ (R ¼ H (2a), Me (2b)) are widely used in organic
synthesis as catalysts for various transformation of alkynes [1]. In
catalytic reactions, labile cyclooctadiene and acetonitrile ligands
are replaced by alkynes while cyclopentadienyl ligand remains
intact thus stabilizing active ruthenium center. The catalytic
behavior of complexes with Cp and Cp* ligands is considered to be
similar, although the activity and selectivity of the unsubstituted
congeners are sometimes diminished [2]. Herein we report the
reactions of 1a and 2a with phenylacetylene and AcOH which are
strikingly different from the analogous reactions of the pentam-
ethylated congeners 1b and 2b.
2.1. Synthesis and X-ray structures
In 2003, Dixneuf et al. have reported [3] that the cyclooctadiene
complex 1b catalyzes coupling of phenylacetylene with addition of
acetic acid giving 1,4-diphenyl-1-acetoxy-1,3-butadiene (3)
(Scheme 1). The reaction was shown to proceed via intermediate
formation of ruthenacycle Cp*Ru(C4H2Ph2)Cl (4b). We found that
similar reaction of the unsubstituted complex 1a gives only a small
amount of 3 (11% yield). The major product is the unusual binuclear
ruthenium complex CpRu(m-s, : ,s-C6H3Ph3)RuCp (5) with a
h3 h3
bridging flyover ligand C6H3Ph3; it was isolated in 58% yield based
on 1a. The reaction of 1a with phenylacetylene in the absence of
AcOH also gives 5 albeit in a lower yield (27%). Although the
mechanism of these reactions is unclear, one can assume that 1a is
first converted into ruthenacycle CpRu(C4H2Ph2)Cl (4a) as reported
by Singleton et al. [4]. Intermediate 4a is less electron rich than its
Cp* congener 4b and therefore it is not protonated by AcOH to give
3. On the other hand, 4a is less hindered than 4b, explaining its
further reaction with the second [CpRu] fragment and phenyl-
acetylene to give 5.
* Corresponding author. Tel.: þ7 499 135 9367; fax: þ7 499 135 5085.
E-mail address: arkudinov@ineos.ac.ru (A.R. Kudinov).
0022-328X/$ e see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2013.03.043

22
D.S. Perekalin et al. / Journal of Organometallic Chemistry 737 (2013) 21e25
ꢀ
and Ru2eC6
s-bonds (av. 2.073 A) are shorter than Ru1eC6 and
ꢀ
ꢀ
Ru2eC1 -bonds (av. 2.120 A). The Ru1eRu2 distance 2.728 A
p
qualifies for a single bond, which is required by 18-electron rule.
The overall geometry of dihydroindene derivative 6 is unremark-
ꢀ
able except for the C3AeC7A bond (1.570 A) which is elongated due
to the ring strain.
2.2. Calculated mechanism of the Cp ligand cleavage
Chart 1. Catalytically active complexes 1a,b and 2a,b.
We have evaluated a possible mechanism of Cp ligand cleavage
in 2a using relativistic DFT calculations at the PBE/L1 level (Fig. 3).
The first step is a simple substitution of two MeCN ligands in 2a by
phenylacetylene molecules to give 8; this step proceeds via a
dissociative mechanism as established by experimental kinetic
studies [11]. Further coupling of two alkynes to give metallacycle 7
proceeds via transition state TS1 with a low activation barrier of
8.6 kcal molꢀ1 (Gibbs energies at 298 K are given). This is similar to
10.0 kcal molꢀ1 barrier calculated by Kirchner et al. for the for-
mation of similar metallacycle [CpRu(C4H4)(MeCN)]þ from 2a and
acetylene [9]. Subsequent addition of MeCN ligand to 7 has a higher
barrier of 14.7 kcal molꢀ1 (TS2) due to the negative entropy
contribution. The incoming MeCN ligand adds two electrons to the
ruthenium center, transforming the Ru]C double bonds in 7 into
more labile RueC single bonds in intermediate IM1. This promotes
subsequent migration of one vinyl carbon atom to the Cp ring via
transition state TS3 (barrier 10.8 kcal molꢀ1) giving intermediate
A few examples of complexes with bridging flyover ligands
analogous to 5 were reported previously [5]. In particular, the co-
balt complexes (OC)2Co( -C6R6)Co(CO)2 were isolated as
m-s
,
h3 h3
:
,s
by-products of catalytic cyclotrimerization of alkynes in the pres-
ence of Co2(CO)8 [6]. However, despite the intensive studies of re-
actions of the cyclopentadienyl ruthenium complexes with alkynes
[1,7], the formation of 5 was not described earlier. The only similar
ruthenium flyover complex CpRu(
RuCp was accidentally obtained by substitution of the carbonyl
m-s, : ,s-C6Ph2(COOMe)4)
h3 h3
ligand in CpRu(m-CO)(m-C2Ph2)RuCp with dimethyl acetylenedi-
carboxylate [8].
The reaction of the acetonitrile complex 2a with phenyl-
acetylene and AcOH in THF also gives 5 (38% yield) [9]. However,
the same reaction in acetonitrile affords dihydroindene derivative 6
(65% yield) as a result of an unusual cleavage of Cp ligand
(Scheme 2). The positions of phenyl substituents in 6 suggest that it
is formed via decomposition of the tentative metallacycle 7.
Apparently strong coordinating ability of acetonitrile solvent fa-
cilitates the displacement of Cp ligand from 7 to give 6 (vide infra).
Noteworthy the Cp cleavage occurs at room temperature. To the
best of our knowledge similar process has been previously
observed only for cyclopentadienyl-carboranyl ruthenium com-
plexes and titanocenes [10]. As expected, Cp* ligand is not cleaved
under similar conditions: the reaction of phenylacetylene and
AcOH in the presence of 2b in acetonitrile produces 3 in 69% yield
(cf. 90% in the case of 1b [3]).
IM2 with h
4-coordination of the cyclopentadiene ligand. It should
be noted that the change of coordination mode of Cp ligand was
previously suggested as an important step of some catalytic re-
actions [12]. However, it generally does not lead to the cleavage of
Cp ligand, which is observed in this case.
The addition of another MeCN ligand to IM2 giving IM3 pre-
sumably has a negligible barrier which we could not locate using
various transition state search techniques. Note that this addition is
favorable by 4.7 kcal molꢀ1 despite the negative entropy contri-
bution. Again the incoming MeCN converts Ru]C bond in IM2 into
RueC bond in IM3. The cleavage of this bond via TS4 (barrier
9.6 kcal molꢀ1) gives complex 9. On the further stages the h2 h3
, -
The structures of compounds 5 and 6 were unambiguously
established by the X-ray diffraction analysis (Figs. 1 and 2). The
overall geometry of complex 5 is consistent with the proposed
dihydroindenyl ligand in 9 is apparently protonated by AcOH and
then replaced by additional MeCN ligands giving 6. Generally
similar mechanism was recently calculated for Cp ring trans-
formation in cyclopentadienyl-carboranyl ruthenium complexes
[10c].
s
,
h3
:
h3
,
s
-coordination of flyover bridging ligand C6H3Ph3 (Scheme
2
ꢀ
1). In particular, C3eC4 distance (1.497 A) is typical for C(sp )e
C(sp2) single bond while C1eC2, C2eC3, C4eC5, and C5eC6 bonds
ꢀ
(av. 1.425 A) have significant double bond character. The Ru1eC1
Scheme 1. The reactions of the cyclooctadiene complexes 1a,b with phenylacetylene
Scheme 2. The reactions of the acetonitrile complexes 2a,b with phenylacetylene and
and AcOH.
AcOH.

D.S. Perekalin et al. / Journal of Organometallic Chemistry 737 (2013) 21e25
23
responsible for generally lower catalytic activity of CpRu complexes
as compared with their Cp*Ru congeners.
4. Experimental details
4.1. General
All reactions were carried out under argon atmosphere in dry
solvents using standard Schlenk techniques. The isolation and
separation of products was conducted in air using preparative TLC
on standard MachereyeNagel silica N/UV254 with fluorescent in-
dicator. Phenylacetylene and acetic acid were purchased from Acros
and used as received. Complexes CpRu(cod)Cl [13,14], [CpRu(-
MeCN)3]BF4 [15], and [Cp*Ru(MeCN)3]PF6 [16] were prepared ac-
cording to the literature procedures. The 1H and 13C NMR spectra
were recorded in CDCl3 with Bruker Avance 600 spectrometer. The
chemical shifts are given in ppm relative to internal SiMe4.
4.2. Synthesis of 1,4-diphenyl-1-acetoxy-1,3-butadiene (3)
The solution of [Cp*Ru(MeCN)3]PF6 (25 mg, 0.05 mmol), phe-
nylacetylene (110 mL, 1 mmol) and acetic acid (29 mL, 0.5 mmol) in
Fig. 1. The structure of 5 with ellipsoids at 50% probability level (only one independent
MeCN (4 ml) was stirred at room temperature overnight. The
resulting green mixture was evaporated to dryness and the product
was purified by preparative TLC using hexaneeEtOAc (10:1)
mixture as eluent to give 3 as a colorless oil which slowly becomes
solid (91 mg, 69% yield). In addition 23 mg of green organometallic
product was isolated by elution of TLC plate with CH2Cl2eEtOH
(1:1) mixture. However we could not identify this product. For 3 1H
molecule is shown). All hydrogen atoms and the Ph substituent at the C3 atom are
omitted for clarity. Selected interatomic distances (A): Ru1eC1 2.078(3), Ru1eC4
2.162(3), Ru1eC5 2.129(3), Ru1eC6 2.121(3), Ru2eC1 2.120(3), Ru2eC2 2.147(3), Ru2e
C3 2.195(3), Ru2eC6 2.067(3), Ru1eRu2 2.7281(3), C1eC2 1.424(4), C1eC7 1.485(4),
C2eC3 1.422(4), C3eC4 1.497(4), C4eC5 1.415(4), C5eC6 1.441(4), C6eC19 1.476(4),
Ru1eRu2 2.728, Ru1/C5 1.875, Ru2/C5 1.880.
ꢀ
NMR:
d
¼ 2.24 (s, 3H, Ac), 6.31 (d, 1H, J ¼ 11 Hz), 6.70 (d, 1H
The overall transformation of 2a into
9 is favorable by
37.3 kcal molꢀ1. The calculated moderate barriers are in accordance
with the observed facile reaction at room temperature. The pro-
posed mechanism also makes clear why the Cp ring cleavage in 2a
does not occur in THF solution. THF is too weak and bulky ligand
and therefore does not add to 7. An attempt to optimize the
structure of hypothetical intermediate IM1-THF (see bottom of
Fig. 3) results in extrusion of THF ligand giving 7.
J ¼ 16 Hz), 7.00 (dd, 1H, J ¼ 11, 16 Hz), 7.20e7.55 (m, 10H, Ph). Cf.
[3a].
4.3. Synthesis of CpRu(m-C6H3Ph3)RuCp (5)
To a solution of CpRu(cod)Cl (61 mg, 0.2 mmol) in THF (4 ml),
phenylacetylene (438 L, 4 mmol) and acetic acid (114 L, 2 mmol)
m
m
were added. The initial red color changes to dark green and then
back to red after 2 h. The mixture was stirred at room temperature
overnight and then analyzed by TLC, which shows the presence of
compounds 3 and 5, but not 6. The mixture was evaporated to
dryness and products were separated by preparative TLC using
hexaneeEtOAc (10:1) mixture as eluent to give red crystals of 5
(37 mg, 58% yield) and 3 as a white solid (55 mg, 11% yield). Similar
reaction in MeCN or CH2Cl2 gives 5 in ca. 50% yield. Similar reaction
3. Conclusion
This study revealed a case of striking difference between re-
actions of CpRu and Cp*Ru complexes with alkynes. While the
Cp*Ru complexes 1b and 2b catalyze coupling of phenylacetylene
with addition of acetic acid, the CpRu congeners 1a and 2a are
involved in stoichiometric transformations interrupting the cata-
lytic cycle. In particular, both theoretical and experimental data
show that the unusual cleavage of Cp ligand in 2a occurs in strongly
coordinating solvent MeCN. Such transformations may be
in the absence of AcOH gives 5 in 27%. 1H NMR:
d
¼ 3.65 (d, 1H,
J ¼ 3.2 Hz), 4.13 (s, 5H, Cp), 4.41 (s, 5H, Cp), 5.18 (dd, 1H, J ¼ 0.9,
3.2 Hz), 5.78 (d, 1H, J ¼ 0.9 Hz), 6.98 (t, 1H, J ¼ 7 Hz), 7.11 (t, 2H,
J ¼ 7 Hz), 7.16e7.26 (m, 4H), 7.33e7.37 (m, 4H), 7.52e7.65 (m, 4H).
13C NMR:
d
¼ 185.66 (RueC), 181.13 (RueC), 156.79, 156.72, 145.98,
128.93, 127.98, 127.39, 127.35, 125.40, 125.37, 124.75, 124.00, 88.49,
86.01 (Cp), 85.57, 84.54 (Cp), 83.94, 69.07. Anal. calcd. for C34H28Ru2
(638.73): C 63.93, H 4.42; found C 64.02, H 4.26.
4.4. Synthesis of 4,7-diphenyl-3a,7a-dihydro-1H-indene (6)
To a solution of [CpRu(MeCN)3]BF4 (75 mg, 0.2 mmol) in MeCN
(4 ml), phenylacetylene (438 mL, 4 mmol) and acetic acid (114 mL,
2 mmol) were added changing the color from orange to dark red.
The mixture was stirred at room temperature for 2 days and then
analyzed by TLC, which shows the presence of compound 6, but not
3 and 5. The mixture was evaporated to dryness and the product
was purified by preparative TLC using hexaneeEtOAc (10:1)
mixture as eluent to give 6 as colorless crystals (35 mg, 65% yield).
Fig. 2. The structure of 6 with ellipsoids at 50% probability level (only one indepen-
dent molecule is shown). All hydrogen atoms and disordered part of the molecule are
ꢀ
omitted for clarity. Selected interatomic distances (A): C1eC2 1.272(8), C1eC7A
1.546(2), C2eC3 1.558(8), C3AeC4 1.520(2), C3AeC3 1.544(2), C3AeC7A 1.570(2), C4e
C5 1.351(2), C4eC8 1.486(2), C5eC6 1.452(2), C6eC7 1.350(2), C7AeC7 1.517(2), C7e
C14 1.484(2).
1H NMR:
d
¼ 2.47 (ddq,1H, J ¼ 2, 7,16 Hz), 2.94 (dd, 1H, J ¼ 9, 16 Hz),

24
D.S. Perekalin et al. / Journal of Organometallic Chemistry 737 (2013) 21e25
Fig. 3. The calculated mechanism for conversion of 2a into 9. Gibbs energies at 298 K are given in kcal molꢀ1 relative to initial reactants, 2a þ 2PhC^CH. Activation barrier values
are given in italic near the lines.
ꢀ
3.88 (dt, 1H, J ¼ 8, 12 Hz), 4.40 (d, 1H, J ¼ 12 Hz), 5.85 (m, 2H), 6.31
(dd, 1H, J ¼ 2, 6 Hz), 6.42 (d, 1H, J ¼ 6 Hz), 7.26e7.32 (m, 2H), 7.36e
7.42 (m, 4H), 7.50e7.59 (m, 4H). Anal. calcd. for C21H18 (270.37): C
93.29, H 6.71; found C 93.50, H 6.52. Compound 6 was reported
earlier, but no details were given [17]. The related 4,7-substituted
3a,7a-dihydro-1H-indenes were described in detail [18].
radiation (
l
¼ 0.71073 A,
u-scans) at 100 K. The structures were
solved by direct method and refined by the full-matrix least-
squares against F2 in anisotropic approximation for non-hydrogen
atoms. The positions of hydrogen atoms were calculated, and
they were refined in isotropic approximation in riding model.
Crystal data and structure refinement parameters for 5 and 6 are
given in Table 1. All calculations were performed using the SHELXTL
software [19].
4.5. X-ray crystallography
4.6. DFT calculations
X-ray diffraction experiments were carried out with a SMART
APEX2 CCD diffractometer using graphite monochromated Mo-K
a
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
Table 1
Crystal data and structure refinement parameters for 5 and 6.
Compound
5
6
Formula
Formula weight
T
C
34H28Ru2
C21H18
270.35
100
double-z basis set L1 augmented by one polarization function was
638.70
100
used [25]. Frequency calculations were performed to confirm the
nature of the stationary points. The paths of the reactions were
traced from the transition states to the products and to the re-
actants using the Intrinsic Reaction Coordinate method (IRC) [26].
The ChemCraft software was used for molecular modeling and
visualization [27]. Cartesian coordinates for optimized structures
are available as supplementary material to this article.
System
Monoclinic
P21/n
Monoclinic
P21/n
Space group
ꢀ
a (A)
13.9896(4)
16.5718(5)
23.4484(8)
97.1090(10)
5394.3(3)
8 (2)
14.5487(10)
7.8871(6)
24.8845(18)
90.6270(10)
2855.3(4)
8 (2)
ꢀ
b (A)
ꢀ
c (A)
ꢁ
b
,
3
ꢀ
V (A )
Z (Z0)
m
, mmꢀ1
11.4
0.71
Acknowledgments
F(000)
2560
1.573
58
1152
1.258
58
Dcalcd (g cmꢀ1
)
2
qmax < (ꢁ)
This work was partially supported by the Ministry of Education
and Science of Russian Federation (grant # 8435).
Reflns measured
Independent reflns [Rint
Obsd reflns [I > 2
Final R(Fhkl): R1
wR2
64,675
14,338
11,023
0.0365
0.0771
1.016
44,171
7598
4934
0.0597
0.1832
1.006
]
s
(I)]
Appendix A. Supplementary material
GOF
Drmax
CCDC 921683 and 921684 contain the supplementary crystal-
lographic data for this paper. These data can be obtained free of
ꢀꢀ3
Drmin (e A
,
)
1.102/e1.169
0.423/e0.346

D.S. Perekalin et al. / Journal of Organometallic Chemistry 737 (2013) 21e25
25
[9] Similar reaction in absence of AcOH was reported to give [CpRu(1,2,4-
Ph3C6H3)]þ cation: E. Rüba, R. Schmid, K. Kirchner, M.J. Calhorda J. Organomet.
Chem. 682 (2003) 204e211.
charge from The Cambridge Crystallographic Data Centre via www.
ccdc.cam.ac.uk/data_request/cif.
[10] (a) A. Tillack, W. Baumann, O.C. Lefeber, A. Spannenberg, R. Kempe,
U. Rosenthal, J. Organomet. Chem. 520 (1996) 187e193;
(b) T. Takahashi, Y. Kuzuba, F. Kong, K. Nakajima, Z. Xi, J. Am. Chem. Soc. 127
(2005) 17188e17189;
Appendix B. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jorganchem.2013.03.043.
(c) Y. Sun, H.-S. Chan, H.T. Zhao, Z.Y. Lin, Z.W. Xie, Angew. Chem. Int. Ed. 45
(2006) 5533e5536;
(d) T. Takahashi, Z. Song, K. Sato, Y. Kuzuba, K. Nakajima, K. Kanno, J. Am.
Chem. Soc. 129 (2007) 11678e11679;
(e) For review see: R. Liu, X. Zhou J. Organomet. Chem. 692 (2007) 4424e
4435.
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