Synthesis of cyclohexadienyl ruthenium complexes by replacement of the naphthalene ligand in [(η5-C6H3Me4)Ru(η6-C10H8)]+

Article abstract of DOI:10.1016/j.jorganchem.2015.03.008

Reactions of the cyclohexadienyl ruthenium complex [(η⁵-C₆H₃Me₄)Ru(C₁₀H₈)]⁺ (1) with 2-electron ligands L lead to replacement of the naphthalene ligand with formation of the half

Full text of DOI:10.1016/j.jorganchem.2015.03.008

Accepted Manuscript
Synthesis of cyclohexadienyl ruthenium complexes by replacement of the
5
6
+
naphthalene ligand in [(η -C H Me )Ru(η -C H )]
6 3 10 8
4
Evgeniya A. Trifonova, Dmitry S. Perekalin, Natalia L. Loskutova, Yulia V. Nelyubina,
Alexander R. Kudinov
PII:
S0022-328X(15)00147-3
10.1016/j.jorganchem.2015.03.008
JOM 18959
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 3 February 2015
Revised Date: 4 March 2015
Accepted Date: 9 March 2015
Please cite this article as: E.A. Trifonova, D.S. Perekalin, N.L. Loskutova, Y.V. Nelyubina, A.R.
Kudinov, Synthesis of cyclohexadienyl ruthenium complexes by replacement of the naphthalene
5
6
+
ligand in [(η -C H Me )Ru(η -C H )] , Journal of Organometallic Chemistry (2015), doi: 10.1016/
6 3 10 8
4
j.jorganchem.2015.03.008.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT
Graphical abstract: synopsis
Half-sandwich cyclohexadienyl ruthenium complexes were synthesized by replacement of the
naphthalene ligand in the readily available complex [(η5-C6H3Me4)Ru(η6-C10H8)]+.

Synthesis of cyclohexadienyl ruthenium complexes
ACCEPTED MANUSCRIPT
by replacement of the naphthalene ligand in [(η5-C6H3Me4)Ru(η6-C10H8)]+
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. E-mail: arkudinov@ineos.ac.ru
Abstract
Reactions of the cyclohexadienyl ruthenium complex [(η5-C6H3Me4)Ru(C10H8)]+ (1) with 2-
electron ligands L lead to replacement of the naphthalene ligand with formation of the half-
t
sandwich complexes [(η5-C6H3Me4)RuL3]+ (L = MeCN, BuNC, P(OEt)3, 1,3,5-triaza-7-
phosphaadamantane). Similar reactions with P(OMe)3 or dppe in the presence of Cl– give the
neutral complexes (η5-C6H3Me4)Ru(P(OMe)3)2Cl or (η5-C6H3Me4)Ru(dppe)Cl, respectively.
Cation 1 also exchanges the naphthalene ligand for other arenes producing the corresponding
sandwich compounds [(η5-C6H3Me4)Ru(arene)]+ (arene = C6H6, 1,4-C6H4(OMe)2). Complex 1
catalyzes cyclotrimerization of N,N-di(propargyl)tosylamide with 1-octyne or 4-pentynol, but
less effectively than [CpRu(C10H8)]+. The mechanism of the naphthalene replacement in 1 was
studied by DFT calculations.
Keywords: Cyclohexadienyl / Ruthenium / Naphthalene / Cyclotrimerization / Alkynes / DFT
calculations
Introduction
Cyclopentadienyl ruthenium complexes (C5R5)RuL2X and [(C5R5)RuL3]+ are widely used
in organometallic synthesis and catalysis [1]. Although analogous cyclohexadienyl complexes
can find similar application, their chemistry is notably less developed. Several compounds with
the unsubstituted cyclohexadienyl ligand [(C6H7)RuL3]+ were obtained by nucleophilic addition
of hydride to the corresponding benzene complexes [2]. Complexes with 6,6-dimethyl-
cyclohexadienyl ligand (η5-C6H5Me2)RuL2Cl have been synthesized by reaction of the sandwich
compound (η5-C6H5Me2)2Ru with HCl followed by addition of 2-electron ligands L [3]. Similar
reaction of (η5-C6H5Me2)2Ru with HBF4 in MeCN has given cationic complex [(η5-
1

C6H5Me2)Ru(MeCN)3]+, in which two acetonitrile ligands can be replaced for PMe3 or dppe.
ACCEPTED MANUSCRIPT
Some related pentadienyl compounds were also obtained by this protonation-substitution
approach [4]. To the best of our knowledge, the catalytic activity of the cyclohexadienyl
complexes was not investigated.
Recently it has been shown that the cyclopentadienyl ruthenium complexes
(C5R5)RuL2X, [(C5R5)RuL3]+ and [(C5R5)Ru(arene)]+ can be conveniently synthesized by
replacement of the naphthalene ligand in the cationic complexes [(C5R5)Ru(C10H8)]+ [5,6,7].
Herein we describe a similar synthesis of the cyclohexadienyl complexes by naphthalene
replacement in the readily available cation [(η5-C6H3Me4)Ru(C10H8)]+ [8]. DFT calculations on
the mechanism of naphthalene replacement in 1 as well as investigation of the catalytic activity
of 1 are also reported.
Results and Discussion
We found that cation [(η5-C6H3Me4)Ru(C10H8)]+ (1) reacts with 2-electron ligands L
t
giving cationic complexes [(η5-C6H3Me4)RuL3]+ (2a–d; L = MeCN, BuNC, P(OEt)3, 1,3,5-
triaza-7-phosphaadamantane) in 68–97% yields (Scheme 1).* The reaction rate depended on the
t
ligand size: small MeCN and BuNC reacted at room temperature, while heating at 60 °С was
required for bulky P(OEt)3 and 1,3,5-triaza-7-phosphaadamantane. Even more bulky ligands,
Ph3P and Ph3Sb, replaced naphthalene ligand in 1 at 60 °С giving mixtures of unidentified
products instead of the expected tris-ligand complexes [9]. Regardless the nature of the ligand,
the naphthalene replacement in 1 proceeded faster than in its cyclopentadienyl analogue
[CpRu(C10H8)]+ [5a, 6b]. This tendency was previously observed for other dienyl complexes
[(η5-C6H7)Ru(C10H8)]+ [10] and [(η5-C8H11)Ru(C10H8)]+ [11].
–
* All cationic complexes described in this paper were isolated and used as salts with PF6 anions.
2

+
ACCEP+TED MANUSCRIPT
L
Ru
L
Ru
L
L
2a L = MeCN, 76%
2b L = tBuNC, 84%
2c L = P(OEt)3, 68%
1
Cl
P(OMe)3
Cl
2d L =
1,3,5-triaza-
7-phospha-
adamantane,
dppe
97%
Ru
Ru
Cl
Cl
PPh2
P(OMe)3
Ph2P
P(OMe)3
3a, 58%
3b, 65%
Scheme 1
Cation 1 also reacted with chloride anion in the presence of P(OMe)3 or dppe in CH2Cl2
at room temperature giving neutral complexes (η5-C6H3Me4)Ru(P(OMe)3)2Cl (3a) or (η5-
C6H3Me4)Ru(dppe)Cl (3b), respectively. The conversion of 1 into 3a,b was quantitative
1
according to H NMR, but the isolated yields were only ca. 60% since high solubility of the
products led to losses during work-up.
The naphthalene ligand in cation 1 can be exchanged for 6-electron ligands, viz. benzene,
1,4-dimethoxybenzene or cycloheptatriene, providing complexes [(η5-C6H3Me4)Ru(C6H6)]+ (4a),
[(η5-C6H3Me4)Ru(1,4-C6H4(OMe)2)]+ (4b) or [(η5-C6H3Me4)Ru(C7H8)]+ (5), respectively
(Scheme 2). The replacement of naphthalene by benzene in acetone solution was slow at room
temperature (50% conversion in a week) and reasonably fast at 60 °C (100% conversion in 24 h).
However, similar reaction with a sterically hindered durene did not reach the complete
conversion even after 96 h of heating at 60 °C. An attempt to accelerate the reaction by visible
light irradiation was unsuccessful. Therefore, we concluded that the arene complexes [(η5-
C6H3Me4)Ru(arene)]+ are more conveniently prepared from dimethyloctadienyl ruthenium
chloride [(ꢀ-η3:η3-C10H16)RuCl2]2 [8] rather than from 1.
3

+
+
ACCEPTED MANUSCRIPT
arene
Ru
Ru
acetone
60 C
Rn
1
arene = C6H6 (4a, 83%),
1,4-C6H4(OMe)2 (4b, 55%)
acetone
60 C
C7H8
+
Ru
5, 94%
Scheme 2
All new compounds were characterized by 1H and 13C NMR spectra as well as elemental
analysis. The structures of complexes [2d]PF6 and 3a were established by X-ray diffraction (Fig.
1 and 2). The coordination of the cyclohexadienyl ligand in the chloride 3a is unsymmetrical
apparently due to the trans-influence of the phosphite ligand. In particular, the Ru1–C6 bond
(2.358 Å), which is located opposite to the P2 atom, is longer than the formally equivalent Ru–
C2 bond (2.203 Å). More symmetrical coordination was observed for the cyclohexadienyl ligand
in 2d where the Ru–C bonds had fallen into a narrow range of 2.260–2.281 Å.
4

Fig. 1. The structure of complex [2d]PF6 in 50% thermal ellipsoids. All hydrogen atoms and the
ACCEPTED MANUSCRIPT
counter-anion are omitted for clarity. Selected interatomic distances (Å): Ru1–C1 2.281(4),
Ru1–C2 2.260(4), Ru1–C4 2.274(4), Ru1–C5 2.263(4), Ru1–C6 2.261(4), Ru1–P1 2.3054(10),
Ru1–P2 2.3018(10), Ru1–P3 2.3271(10).
Fig. 2. The structure of 3a in 50% thermal ellipsoids. All hydrogen atoms are omitted for clarity.
Selected interatomic distances (Å): Ru1–C2 2.203(4), Ru1–C3 2.183(4), Ru1–C4 2.217(4), Ru1–
C5 2.290(4), Ru1–C6 2.358(4), Ru1–P1 2.2654(11), Ru1–P2 2.2448(10), Ru1–Cl1 2.4556(10).
It has been recently shown that the cyclopentadienyl ruthenium naphthalene complexes
[(C5R5)Ru(C10H8)]+ are efficient catalysts for various transformations of alkynes due to their
ability to generate active species [(C5R5)Ru]+ [5a,6b,12]. In contrast, we found that the
cyclohexadienyl complexes 1 and 2a were generally inactive in such catalytic reactions. In
particular, they did not promote Alder-ene reaction between 3-hexyne and N-tosyl-allylamine
[13], addition of acetic acid to phenylacetylene [14,15], as well as anti-Markovnikov hydration
of phenylacetylene in the presence of bipyridine [12b]. In the presence of Cl– anion complex 1
catalyzed cyclotrimerization of N,N-di(propargyl)tosylamide (6) with 1-octyne or 4-pentynol
giving isoindoline derivatives 7a,b in good yields (Scheme 3). However, compared to the
cyclopentadienyl analogue [CpRu(C10H8)]+, higher loading of catalyst 1 (5%) and longer
reaction times (2–6 h) were required to achieve full conversion of 6.
5

ACCEPTED MANUSCRIPT
Scheme 3
It was mentioned above that the naphthalene replacement in the cyclohexadienyl
complexes [(η5-C6H3R4)Ru(C10H8)]+ (R = H, Me) proceeds faster than in the cyclopentadienyl
analogue [CpRu(C10H8)]+. We have studied the mechanism of naphthalene replacement by
MeCN in the parent complexes [(η5-C6H7)Ru(C10H8)]+ and [CpRu(C10H8)]+ by DFT
computation. Figure 3 shows the intrinsic reaction coordinates (IRC) for the primary step, at
which these species are attacked by the first MeCN molecule. This step has maximal activation
energy, since it is changes the coordination mode of the naphthalene ligand from η6 in complex
to η4 in transition state TS and intermediate IM (Figure 4). It is in accordance with general
tendency established earlier both experimentally [16] and theoretically [6b] for chromium and
ruthenium naphthalene complexes. The activation energy of naphthalene replacement in the
cyclohexadienyl complex is considerably lower than for the cyclopentadienyl analogue (Table
1). These results correlate with previous EDA calculations [8] indicating that stronger Ru–C6H7
bond (vs Ru–Cp) leads to weaker Ru–arene bond in cyclohexadienyl complexes.
Figure 3. Intrinsic reaction coordinates for the primary step of naphthalene replacement by
acetonitrile in [(η5-C6H7)Ru(C10H8)]+ and [CpRu(C10H8)]+ (at PBE/L2 level).
6

ACCEPTED MANUSCRIPT
Figure 4. Optimized structures of the transition state TS (above) and the intermediate IM
(below) for the primary step of naphthalene replacement by acetonitrile in cation [(η5-
C6H7)Ru(C10H8)]+ (at BPBE/L2 level).
Table 1. Activation enthalpies Ha and free energies Ga for the primary step of naphthalene
replacement in [(η5-C6H7)Ru(C10H8)]+ and [CpRu(C10H8)]+ complexes by MeCN. Energies are
given at BPBE/def2-TZVPP//BPBE/L2 level with PCM solvation energy corrections for MeCN
(in kcal mol–1 at 298.15 K).
Complex
Ha
Ga
[(η5-C6H7)Ru(C10H8)]+
[CpRu(C10H8)]+
16.6 26.2
20.7 31.5
Conclusion
To conclude, we have developed a general method for the synthesis of various
cyclohexadienyl ruthenium complexes via naphthalene replacement in the readily available
cation [(η5-C6H3Me4)Ru(C10H8)]+ (1). Both experiment and computation indicate that the
7

naphthalene replacement in the cyclohexadienyl complexes is faster than in cyclopentadienyl
ACCEPTED MANUSCRIPT
analogues. At the same time the catalytic activity of 1 in alkyne transformations is lower than
that of [CpRu(C10H8)]+.
Experimental section
General
All reactions were carried out under argon in anhydrous solvents, which were purified and dried
1
31
using standard procedures. Isolation of products was conducted in air. H, 13С and P NMR
spectra were measured with a Bruker Avance 400 spectrometer at 20°C from [D6]-acetone
solutions of complexes, unless otherwise stated. Complex [1]PF6 was synthesized according to
the published procedure [8].
Synthesis of [(η5-C6H3Me4)Ru(MeCN)3]PF6 ([2a]PF6)
A solution of [1]PF6 (51 mg, 0.10 mmol) in acetonitrile (1 ml) was stirred overnight. Then
hexane (10 mL) was added to extract the liberated naphthalene. The mixture was vigorously
stirred for 5 minutes and the upper phase of the biphasic system was removed. Another portion
of hexane (10 ml) was added to a reaction mixture, it was left stirring for 5 hours. This process
was repeated twice. After a total of 44 h stirring, the acetonitrile solution was evaporated in
vacuum and the resulting green-yellow solid was washed with hexane (3×5 mL) to give [2a]PF6
as a yellow-green solid (38 mg, 0.075 mmol, 76% yield). In order to avoid possible oxidation of
[2a]PF6 its isolation was carried out under argon atmosphere.
1H NMR (400 MHz, CD2Cl2): δ = 5.23 (s, 1H, C6H3Me4), 2.17 (s, 2H, C6H3Me4), 2.12 (s, 9H,
MeCN), 1.65 (s, 6H, Me), 1.32 (s, 3H, Me), 0.29 (s, 3H, Me). 13C NMR (101 MHz): δ = 99.28,
70.20, 44.25, 37.52, 27.65, 19.76, 2.11 (MeCN). Anal. Calc. for C16H24F6N3PRu: C 38.10, H
4.80; found C 38.24, H 4.57.
Synthesis of [(η5-C6H3Me4)Ru(tBuNC)3]PF6 ([2b]PF6)
A solution of [1]PF6 (20 mg, 0.04 mmol) and tBuNC (0.224 mL, 2.00 mmol) was stirred in THF
(2 ml) for 24 hours. The solvent was evaporated, the residue was dissolved in CH2Cl2 and eluted
through a short alumina column (3 cm) with acetone-CH2Cl2 mixture (1:1). Resulting solution
was evaporated, the residue was washed with Et2O-pentane mixture (1:1) and reprecipitated from
CH2Cl2 by Et2O-pentane mixture (1:4) to give white crystals of [2b]PF6 (20 mg, 0.032 mmol,
84% yield).
1H NMR (400 MHz): δ = 5.81 (s, 1H, C6H3Me4) 3.12 (d, J = 1 Hz, 2H, C6H3Me4), 1.94 (s, 6H,
t
13
Me), 1.59 (s, 9H, Bu), 1.37 (s, 3H, Me), 0.55 (s, 3H, Me). C NMR (101 MHz): δ = 143.26
8

(CN), 122.20, 112.82, 78.67, 61.81 (CMe3), 37.09, 35.76, 34.39, 25.27, 21.26 (CMe3). Anal.
ACCEPTED MANUSCRIPT
Calc. for C25H42F6N3PRu×CH2Cl2: C 43.64, H 6.20; found C 43.86, H 6.07.
Synthesis of [(η5-C6H3Me4)Ru(P(OEt)3)3]PF6 ([2c]PF6)
A solution of [1]PF6 (25 mg, 0.050 mmol) and P(OEt)3 (0.05 mL, 0.30 mmol) in acetone (2 ml)
was heated at 60 ºC for 10 hours. The solvent was evaporated and the solid was washed with
Et2O (2×7ml). The residue was dissolved in CH2Cl2, filtered through a piece of cotton wool and
reprecipitated from CH2Cl2 by petroleum ether to give [2c]PF6 (30 mg, 0.034 mmol, 68% yield)
as white solid.
1H NMR (400 MHz): δ = 5.52 (s, 1H, C6H3Me4), 4.18 (dt, J = 7, 5 Hz, 18H, OCH2CH3), 2.96 (s,
2H, C6H3Me4), 2.02 (s, 6H, Me), 1.36 (s, 3H, Me) 1.33 (t, J = 7 Hz, 27H, OCH2CH3), 0.49 (s,
3H, Me). 31P NMR (162 MHz): δ = 137.93 (s), −144.05 (sept, J = 708 Hz, PF6). 13C NMR (101
MHz): δ = 113.71, 80.69, 62.60 – 62.07 (m), 37.55, 36.76, 20.31, 15.50. Anal. Calc. for
C28H60F6O9P4Ru: C 38.23, H 6.87; found C 37.92, H 6.88.
Synthesis of [(η5-C6H3Me4)Ru(1,3,5-triaza-7-phosphaadamantane)3]PF6 ([2d]PF6)
A solution of [1]PF6 (25 mg, 0.050 mmol) and 1,3,5-triaza-7-phosphaadamantane (39 mg, 0.25
mmol) in acetone (2 mL) was heated at 60 ºC for 10 hours. The solvent was evaporated and the
solid was washed with Et2O-petroleum ether mixture (1:1). The residue was dissolved in
acetone, filtered through a piece of cotton wool and reprecipitated from acetone by petroleum
ether to give [2d]PF6 (41 mg, 0.048 mmol, 97% yield) as white solid.
1H NMR (400 MHz): δ = 6.01 (s, 1H, C6H3Me4), 4.66 (d, J = 13 Hz, 9H, CH2), 4.54 (d, J = 13
Hz, 9H, CH2), 4.25 (s, 18H, CH2), 3.09 (s, 2H, C6H3Me4), 2.28 (s, 6H, Me), 1.48 (s, 3H, Me),
31
13
0.51 (s, 3H, Me). P NMR (162 MHz): δ = –42.99 (s), −144.05 (sept, J = 708 Hz, PF6). C
NMR (101 MHz): δ = 108.80, 81.64, 72.32, 57.76 (m), 55.07 (m), 39.91, 21.89. Anal. Calc. for
C28H51F6N9P4Ru: C 39.44, H 6.03; found C 39.98, H 6.31.
Synthesis of (η5-C6H3Me4)Ru(P(OMe3)2Cl (3a)
A solution of [1]PF6 (51 mg, 0.10 mmol), P(OMe)3 (0.1 mL, 0.80 mmol), and [Et3NBn]Cl (23
mg, 0.10 mmol) in CH2Cl2 (2 mL) was stirred overnight. The solvent was evaporated, the residue
was dissolved in CH2Cl2 and eluted through a short alumina column (3 cm) with petroleum
ether-CH2Cl2 mixture (1:1). Resulting solution was evaporated and the residue was washed with
cold pentane (2 ml) to give 3a (30 mg, 0.058 mmol, 58% yield) as yellow solid.
1H NMR (400 MHz): δ = 5.45 (s, 1H, C6H3Me4), 3.73 (m, 18H, OMe), 2.49 (br. s, 2H,
C6H3Me4), 1.79 (s, 6H, Me), 1.22 (s, 3H, Me), 0.42 (s, 3H, Me). 13C NMR (101 MHz): δ = 79.84
9

31
(m), 52.38, 37.07, 35.83 (m), 27.78, 20.85. P NMR (162 MHz, CDCl3): δ = 153.23 (s). Anal.
ACCEPTED MANUSCRIPT
Calc. for C16H33ClO6P2Ru: C 36.96, H 6.40; found C 36.95, H 6.42.
Synthesis of (η5-C6H3Me4)Ru(dppe)Cl (3b)
A solution of [1]PF6 (51 mg, 0.10 mmol), dppe (40 mg, 0.10 mmol), and [Et3NBn]Cl (23 mg,
0.10 mmol) in CH2Cl2 (2 mL) was stirred overnight. The solvent was evaporated and the residue
was extracted with Et2O (2×3 ml). Yellow extract was evaporated and the residue was washed
with cold pentane (2 ml) to give 3b (42 mg, 0.063 mmol, 65% yield) as bright yellow solid.
1H NMR (400 MHz): δ = 7.98 (s, 4H, Ph), 7.41 (m, 6H, Ph), 7.37 (m, 6H, Ph), 7.33-7.25 (m, 4H,
Ph), 5.91 (br. s, 1H, C6H3Me4), 2.98 (dd, J = 13, 6 Hz, 2H, dppe), 2.39 (br. s, 2H, C6H3Me4),
2.14 (br. s, 2H, dppe), 1.42 (s, 6H, Me), 1.16 (s, 3H, Me), 0.43 (s, 3H, Me). 31P NMR (162 MHz,
CDCl3): δ = 68.71 (s). Anal. Calc. for C36H39ClP2Ru: C 64.52, H 5.87; found C 65.06, H 6.02.
Synthesis of [(η5-C6H3Me4)Ru(C6H6)]PF6 ([4a]PF6)
A solution of [1]PF6 (51 mg, 0.10 mmol) and benzene (0.027 ml, 0.30 mmol) in acetone (3 ml)
was heated at 60 ºC for 24 hours. The solvent was evaporated, the residue was dissolved in
CH2Cl2 and eluted through a short alumina column (3 cm) with acetone-CH2Cl2 mixture (1:1).
Resulting solution was evaporated, the solid was washed with Et2O (3×5 ml) and reprecipitated
from CH2Cl2 by Et2O to give white microcrystals of [4a]PF6 (38 mg, 0.083 mmol, 83% yield).
1H NMR (400 MHz): δ = 6.62 (s, 1H, C6H3Me4), 6.36 (s, 6H, C6H6), 3.71 (s, 2H, C6H3Me4), 1.99
(s, 6H, Me), 1.31 (s, 3H, Me), 0.41 (s, 3H, Me). The spectrum is similar to that described in ref.
[8].
Synthesis of [(η5-C6H3Me4)Ru(1,4-C6H4(OMe)2)]PF6 ([4b]PF6)
A solution of [1]PF6 (44 mg, 0.090 mmol) and p-dimetoxybenzene (36 mg, 0.27 mmol) in
acetone (3 ml) was heated at 60 ºC for 24 hours. The solvent was evaporated and the solid was
washed with diethyl ether (3×2ml). The residue was dissolved in CH2Cl2, filtered, and the
product was crystallized by slow diffusion of Et2O vapors into solution to give white crystals of
[4b]PF6 (25 mg, 0.048 mmol, 55% yield).
1H NMR (400 MHz): δ = 6.60 (s, 1H, C6H3Me4), 6.22 (s, 4H, C6H4), 3.90 (s, 6H, OMe), 3.47 (s,
2H, C6H3Me4), 1.90 (s, 6H, Me), 1.34 (s, 3H, Me), 0.42 (s, 3H, Me). 13C NMR (101 MHz): δ =
134.49, 101.13, 88.18, 75.74, 56.76, 54.21, 37.28, 32.94, 19.84. Anal. Calc. for C18H25F6O2PRu:
C 41.62, H 4.85; found C 40.97, H 4.96.
Synthesis of [(η5-C6H3Me4)Ru(C7H8)]PF6 ([5]PF6)
10

A solution of [1]PF6 (51 mg, 0.10 mmol) and cycloheptatriene (0.031 ml, 0.30 mmol) in acetone
ACCEPTED MANUSCRIPT
(3 ml) was heated at 60 ºC for 24 hours. The solvent was evaporated and the solid was washed
with Et2O (3×2 ml). The residue was reprecipitated from CH2Cl2 by Et2O to give yellow crystals
of [5]PF6 (44 mg, 0.093 mmol, 94% yield).
1H NMR (400 MHz): δ = 6.40 (br. s, 2H, C7H8 ), 6.25 (s, 1H, C6H3Me4) 5.80 (br. s, 2H, C7H8),
4.09 (br. s, 2H, C7H8), 3.95 (s, 2H, C6H3Me4), 3.21 (m, 1H, C7H8), 1.86 (s, 6H, Me), 1.67 (m,
13
1H, C7H8), 1.24 (s, 3H, Me), 0.47 (s, 3H, Me). C NMR (101 MHz): δ = 107.21, 98.63, 96.40,
88.04, 60.44, 42.71, 38.35, 34.15, 28.06, 22.96, 19.37. Anal. Calc. for C17H23F6PRu: C 43.13, H
4.90; found C42.63, H 5.01.
Cyclotrimerization of Diyne 6 with 1-octyne
To a solution of [1]PF6 (5 mg, 0.01 mmol), [Et3NBn]Cl (2.3 mg, 0.01 mmol), and 1-octyne
(0.117 ml, 0.80 mmol) in CH2Cl2 (1 ml) a solution of diyne (50 mg, 0.20 mmol) in CH2Cl2 (1
mL) was added dropwise within 30 min. The reaction mixture was stirred for 6 h. After complete
consumption of diyne (by TLC), the solvent was evaporated, and the crude product was purified
by flash column chromatography on silica gel (gradient elution with hexane-EtOAc, from 10:1 to
1:1) to afford pure isoindoline derivative 7a (58 mg, 0.16 mmol, 80% yield).
1H NMR (400 MHz, CDCl3): δ = 7.76 (d, J = 8 Hz, 2H, Ts), 7.30 (d, J = 8 Hz, 2H, Ts), 7.07 (d, J
= 8 Hz, 2H, CH),7.04 (d, J = 8 Hz, 2H, CH), 6.97 (s, 1H, CH), 4.58 (s, 4H, CH2), 2.55 (t, J = 7
Hz, 2H, CH2), 2.40 (s, 3H, CH3), 1.55 (m, 2H, CH2), 1.27 (m, 6H, CH2), 0.87 (t, J = 7 Hz, 3H,
CH3). The spectrum is similar to that described in ref. [17].
Cyclotrimerization of Diyne 6 with 4-pentynol
To a solution of [1]PF6 (5 mg, 0.01 mmol), Et3NBnCl (2.3 mg, 0.01 mmol), and 4-pentynol
(0.074 ml, 0.8 mmol) in CH2Cl2 (1 ml) a solution of diyne (50 mg, 0.20 mmol) in CH2Cl2 (1 ml)
was added dropwise within 30 min. The reaction mixture was stirred for 2 h. After complete
consumption of diyne (by TLC), the solvent was evaporated, and the crude product was purified
by flash column chromatography on silica gel (gradient elution with hexane-EtOAc, from 9:1 to
1:1) to afford pure isoindoline derivative 7b (57 mg, 0.17 mmol, 86% yield).
1H NMR (400 MHz, CDCl3): δ = 7.75 (d, J = 8 Hz, 2H, Ts), 7.30 (d, J = 8 Hz, 2H, Ts), 7.06 (br.
s, 2H, CH), 6.99 (br. s, 1H, CH), 4.56 (s, 4H, CH2), 3.62 (t, J = 6 Hz, 2H, CH2), 2.72–2.60 (m,
2H, CH2), 2.38 (s, 3H, CH3), 1.98 (br. s., 1H, OH), 1.86–1.77 (m, 2H, CH2). The spectrum is
similar to that described in ref. [18].
11

Crystallographic data
ACCEPTED MANUSCRIPT
Crystals of [2d]PF6 (C28H51F6N9P4Ru × 1.4[CH2Cl2], M = 971.62) were triclinic, space group P-
1, at 120K: a = 12.6225(5), b = 12.6611(5), c = 14.2864(5) Å, α = 88.6570(10), β = 72.6870(10),
γ = 68.2030(10)°, V = 2014.11(13) Å3, Z = 2 (Z’ = 2), dcalc = 1.602 g cm–3, µ(MoKα) = 7.98 сm–
1, F(000) = 998. Crystals of 3a (C16H33ClO6P2Ru, M = 519.88) were monoclinic, space group
C2/c, at 120K: a = 16.2380(10), b = 10.2996(6), c = 25.8352(16) Å, β = 96.5950(10)°, V =
4292.2(5) Å3, Z = 8 (Z’ = 1), dcalc = 1.609 g cm–3, µ(MoKα) = 10.32 сm–1, F(000) = 2144.
Intensities of 20883 and 14298 reflections for [2d]PF6 and 3a, respectively, were measured with
a Bruker APEX2 CCD diffractometers [λ(MoKα) = 0.71072Å, ω-scans, 2θ<54°]. 8794 and
4674 independent reflections [Rint 0.0390 and 0.0261] were used in further refinement for
[2d]PF6 and 3a, respectively. The structures were solved by direct method and refined by the
full-matrix least-squares technique against F2 in the anisotropic-isotropic approximation. The
H(C) atom positions were calculated, and they were refined in the isotropic approximation
within riding model. For [2d]PF6, the refinement converged to wR2 = 0.1634 and GOF = 1.206
for all the independent reflections (R1 = 0.0545 was calculated against F for 7561 observed
reflections with I>2σ(I)). For 3a, the refinement converged to wR2 = 0.1243 and GOF = 1.005
for all the independent reflections (R1 = 0.0446 was calculated against F for 4046 observed
reflections with I>2σ(I)). All calculations were performed using SHELXTL PLUS 5.0 [19].
Computation details
Geometry optimizations were performed without constraints using PBE and BPBE exchange-
correlation functionals [20], the scalar-relativistic Hamiltonian [21], atomic basis sets of
generally-contracted Gaussian functions [22] and a density-fitting technique [23] as implemented
in a recent version of Priroda code [24]. The all-electron triple-ζ basis set L2 (similar to cc-
pVTZ) [25] augmented by two polarization functions was used [26]. Frequency calculations
were performed to confirm the nature of the stationary points to yield one imaginary frequency
for the transition states and none for the minima. The path of the reaction was traced from the
transition state to the product and back to the reactant by using the Intrinsic Reaction Coordinate
method (IRC) [27]. The Gibbs free energy values were obtained from frequency calculation
using BPBE functional, triple-ζ basis set augmented by two polarization functions def2-TZVPP
[28] and solvent corrections for MeCN according to PCM model [29] as implemented in
Gaussian 09 software [30]. The ChemCraft software [31] was used for molecular modeling and
visualization.
12

Acknowledgments
ACCEPTED MANUSCRIPT
The work was supported by the Russian Foundation for Basic Research (grant # 14-03-32044)
and the grant for young scientists of the President of Russian Federation (grant # MK-
4261.2014.3).
Appendix A. Supplementary material
CCDC 1046330 ([2d]PF6) and 1046331 (3a) contain 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/data_request/cif.
Appendix B. Supplementary material
Supplementary data associated with this article can be found online.
Graphical abstract
References
1
For reviews see: a) S. Derien, Top. Organomet. Chem. 48 (2014) 289; b) B.M. Trost, M.U.
Frederiksen, M.T. Rudd, Angew. Chem., Int. Ed. 44 (2005) 6630; c) C. Slugovc, E. Rüba, R.
Schmid, K. Kirchner, K. Mereiter, Monatsh. Chem. 131 (2000) 1241; d) S.G. Davies, J.P.
McNally, A.J. Smallridge, Adv. Organomet. Chem. 30 (1990) 1.
2
See for example: a) H. Mishra, A.K. Patra, R. Mukherjee, Inorg. Chim. Acta 362 (2009) 483;
b) D.R. Robertson, I.W. Robertson, T.A. Stephenson, J. Organomet. Chem. 202 (1980) 309.
3 P.T. Dimauro, P.T. Wolczanski, Polyhedron 14 (1995) 149.
4 a) A. Bauer, U. Englert, S. Geyser, F. Podewils, A. Salzer, Organometallics 19 (2000) 5471; b)
T. Lumini, D.N. Cox, R. Roulet, K. Schenk, J. Organomet. Chem. 434 (1992) 363.
13

ACCEPTED MANUSCRIPT
5 For pioneer works see: a) L. Hintermann, L. Xiao, A. Labonne, U. Englert, Organometallics 28
(2009) 5739; b) E.P. Kündig, F.R. Monnier, Adv. Synth. Catal. 346 (2004) 901.
6
a) D.S. Perekalin, N.V. Shvydkiy, Y.V. Nelyubina, A.R. Kudinov, Mendeleev Commun. 25
(2015) 29; b) D.S. Perekalin, E.E. Karslyan, E.A. Trifonova, A.I. Konovalov, N.L. Loskutova,
Y.V. Nelyubina, A.R. Kudinov, Eur. J. Inorg. Chem. (2013) 481; c) D.S. Perekalin, E.E.
Karslyan, P.V. Petrovskii, A.O. Borissova, K.A. Lyssenko, A.R. Kudinov, Eur. J. Inorg. Chem.
(2012) 1485; d) 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.
7 For review see: D.S. Perekalin, A.R. Kudinov, Coord. Chem. Rev. 276 (2014) 153.
8 E.A. Trifonova, D.S. Perekalin, N.L. Loskutova, Y.V. Nelyubina, A.R. Kudinov, J. Organomet.
Chem. 770 (2014) 1.
9
It is interesting to note that less sterically hindered cyclopentadienyl complex [CpRu(C10H8)]+
reacts with PPh3 giving [CpRu(PPh3)3]+. See ref. 5a for details.
10
D.S. Perekalin, E.A. Trifonova, Y.V. Nelyubina, A.R. Kudinov, J. Organomet. Chem. 745
(2014) 1.
11 T. Shibasaki, N. Komine, M. Hirano, S. Komiya, J. Organomet. Chem. 692 (2007) 2385.
12 a) L. Li, S.B. Herzon, Nature Chemistry 6 (2014) 22; b) L. Li, M. Zeng, S.B. Herzon, Angew.
Chem., Int. Ed. 53 (2014) 7892.
13
L. Severa, J. Vávra, A. Kohoutová, M. Cizková, T. Šálová, J. Hyvl, D. Šaman, R. Pohl, L.
Adriaenssens, F. Teply, Tetrahedron Lett. 50 (2009) 4526.
14 J. Le Paih, F. Monnier, S. Derien, P.H. Dixneuf, E. Clot, O. Eisenstein, J. Am. Chem. Soc. 125
(2003) 11964.
15 D.S. Perekalin, E.A. Trifonova, V.V. Novikov, Y.V. Nelyubina, A.R. Kudinov, J. Organomet.
Chem. 737 (2013) 21.
16 a) S. Zhang, J.K. Shen, F. Basolo, T.D. Ju, R.F. Lang, G. Kiss, C.D. Hoff, Organometallics 13
(1994) 3692; b) A.M. McNair, K.R. Mann, Inorg. Chem. 25 (1986) 2519.
17 Y.-H. Wang, S.-H. Huang, T.-C. Lin, F.-Y. Tsai, Tetrahedron 66 (2010) 7136.
18 A.-L. Auvineta, V. Michelet, V. Ratovelomanana-Vidal, Synthesis 45 (2013) 2003.
19 G.M. Sheldrick, Acta Cryst. A 64 (2008) 112.
20 J.P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 177 (1996) 3865.
21 K. G. Dyall, J. Chem. Phys. 100 (1994) 2118.
22 D.N. Laikov, Chem. Phys. Lett. 416 (2005) 116.
23 D.N. Laikov, Chem. Phys. Lett. 281 (1997) 151.
24 D.N. Laikov, Yu.A. Ustynyuk, Russ. Chem. Bull. 54 (2005) 820.
25 Dunning Jr., T. H. J. Chem. Phys. 1989, 90, 1007–1023.
14

ACCEPTED MANUSCRIPT
26 E.Ya. Misochko, A.V. Akimov, V.A. Belov, D.A. Tyurin, D.N. Laikov, J. Chem. Phys. 127
(2007) 084301.
27 K. Fukui, Acc. Chem. Res. 14 (1981) 363.
28 a) F. Weigend, R. Ahlrichs, Phys. Chem. Chem. Phys. 7 (2005) 3297; b) http://bases.turbo-
forum.com/TBL/tbl.html
29 J. Tomasi, B. Mennucci, R. Cammi, Chem. Rev. 105 (2005) 2999.
30
Gaussian 09, Revision A.02, M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A.
Robb, J.R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M.
Caricato, X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M. Hada,
M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H.
Nakai, T. Vreven, J.A. Montgomery, Jr., J.E. Peralta, F. Ogliaro, M. Bearpark, J.J. Heyd, E.
Brothers, K.N. Kudin, V.N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A.
Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J.M. Millam, M. Klene, J.E.
Knox, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev,
A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G.
Zakrzewski, G.A. Voth, P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, Ö. Farkas, J.
B. Foresman, J.V. Ortiz, J. Cioslowski, D.J. Fox, Gaussian, Inc., Wallingford CT, 2009.
31 G.A. Zhurko, ChemCraft 1.6, http://www.chemcraftprog.com.
15

ACCEPTED MANUSCRIPT
Highlights
Cyclohexadienyl ruthenium complexes were synthesized by naphthalene replacement
The mechanism of naphthalene replacement was studied by DFT calculations
Cyclohexadienyl ruthenium naphthalene complex catalyzes cyclotrimerization of alkynes

ACCEPTED MANUSCRIPT
SUPPORTING INFORMATION
Synthesis of cyclohexadienyl ruthenium complexes by replacement of the naphthalene
ligand in [(η5-C6H3Me4)Ru(η6-C10H8)]+
Evgeniya A. Trifonova, Dmitry S. Perekalin, Natalia L. Loskutova, Yulia V. Nelyubina,
Alexander R. Kudinov

ACCEPTED MANUSCRIPT
Cartesian coordinates and energies for structures optimized at PBE/L2 and BPBE/L2.
[(η5-C6H7)Ru(η6-C10H8)]+
PBE/L2
BPBE/L2
E = -5149.543778 a.u.
E0 = -5149.287801 a.u.
E = -5149.910251 a.u.
E0 = -5149.654595 a.u.
ZPVE = 0.255977 a.u. = 160.6281 kcal/mol
T = 298.150 K: H = 169.8031 kcal/mol,
G = 135.4871 kcal/mol
ZPVE = 0.255656 a.u. = 160.4266 kcal/mol
T = 298.150 K: H = 169.6298 kcal/mol,
G = 135.2675 kcal/mol
6
6
6
6
6
6
1
1
1
1
1
1
1
44
6
6
6
6
6
6
6
6
6
6
1
1
1
1
1
1
1
1
-2.35380489
-2.35384197
-1.48362336
-1.48358119
-1.07214080
-3.31316043
-4.13421588
-1.04100354
-0.35923161
-1.04089241
-3.76910797 -0.81134970 -0.00005637
-2.54802248 -0.22843912 -2.08728406
-2.54811398 -0.22850827
-0.53946346 -0.09802808
-0.13205977 -2.18396383
0.31837586 -1.16316602
6
6
6
6
6
6
1
1
1
1
1
1
1
44
6
6
6
6
6
6
6
6
6
6
1
1
1
1
1
1
1
1
-2.36782928
-2.36788240
-1.50267385
-1.50262531
-1.09392393
-3.32894502
-4.15519951
-1.06411600
-0.38755309
-1.06402888
-3.77866221 -0.83152304 -0.00009857
-2.56010183 -0.23807571 -2.09040011
-2.56018916 -0.23830328
-0.54578306 -0.09890142
-0.12366418 -2.18856928
0.30840113 -1.16531808
0.31832693
1.44248767
1.16315128
1.22731385
0.30828081
1.43956739
1.16531600
1.22938280
1.44253843 -1.22727281
2.04510828 0.00004093
0.18610840 -0.00002733
1.43969952 -1.22923855
2.04574602 0.00011295
0.16918773 -0.00003039
0.92581537 -0.00002548
0.90376425 -0.00001157
1.77396312
2.86937225
2.16688614
0.00007690
1.77548754
2.87595004
2.16960764
0.00017639
1.77400805 -2.16681386
1.77571372 -2.16941159
2.08724533
0.00001014
0.70772095
2.09032977
0.00001103
0.70882904
0.70622653 -1.27720681 -1.40962777
1.68386413 -0.47619001 -0.72444163
1.68386046 -0.47616466
-0.13206897 -2.18397484 -0.70768325
0.71211009 -1.27649515 -1.41175104
1.69109623 -0.47250999 -0.72580060
1.69109947 -0.47248820
-0.12370089 -2.18855838 -0.70881436
0.72442976
0.72577204
0.70625030 -1.27719376
1.40964260
1.41544321
0.71078351
0.71211672 -1.27646059
1.41174702
1.41804586
0.71210588
2.62185767
3.53052697
2.62183439
3.53053139
-0.81826461 -2.82955565 -1.25378260
0.66339970 -1.23720080 -2.49833127
0.66344388 -1.23717570
-0.81824219 -2.82954771
4.26415436
2.62338006
4.26414441
2.62339143
0.34649108
1.09794233
2.63478995
3.54862703
2.63495949
3.54873447
-0.80551348 -2.83885140 -1.25534353
0.66958919 -1.23895249 -2.50065762
0.66964094 -1.23896006
-0.80545839 -2.83886547
4.28572217
2.63780726
4.28594714
2.63807622
0.34801703
1.09637690
0.34647891 -1.41547514
1.09791626 -0.71083556
0.34774575 -1.41812988
1.09621668 -0.71223183
2.49834647
1.25383329
1.24405908
2.50604577
2.50065693
1.25537733
1.24558972
2.50882298
1.70256121
0.34371558
1.69729030
0.34555356
1.70253733 -1.24412847
0.34363558 -2.50607758
1.69696398 -1.24573976
0.34509038 -2.50890593
[CpRu(η6-C10H8)]+
PBE/L2
BPBE/L2
E = -5110.275598 a.u.
E0 = -5110.047484 a.u.
E = -5110.622792 a.u.
E0 = -5110.395002 a.u.
ZPVE = 0.228114 a.u. = 143.1435 kcal/mol
T = 298.150 K: H = 151.6292 kcal/mol,
G = 118.4103 kcal/mol
ZPVE = 0.227791 a.u. = 142.9409 kcal/mol
T = 298.150 K: H = 151.4534 kcal/mol,
G = 118.1614 kcal/mol
6
6
6
6
6
1
1
1
1
1
44
6
6
6
6
6
6
6
6
6
6
1
1
1
1
1
-2.62466012
-2.62481562
-1.68568271
-1.68542127
-1.10547444
-1.45630736
-3.24079723 -0.16858675 -1.35696140
-0.34191280
-1.45585724
-3.24109169 -0.16883462
-0.65079565 -0.10560396
-0.31589217 -2.17632404
0.55150416 -1.30712587 -1.41769543
1.51293429 -0.49425729 -0.72592021
1.51295813 -0.49420190
-0.31591651 -2.17637631 -0.71188800
0.55156209 -1.30703059
2.44271288
3.33529653
2.44264017
3.33526180
-1.02584484 -2.79795070 -1.25560577
0.51297560 -1.26802235 -2.50625691
0.45857505 -0.71905723
6
6
6
6
6
1
1
1
1
1
44
6
6
6
6
6
6
6
6
6
6
1
1
1
1
1
-2.63883091
-2.63887719
-1.70737855
-1.70733187
-1.13224834
-1.48168247
-3.25062809 -0.18940435 -1.35827774
-0.37765361
-1.48155479
-3.25066875 -0.18946175
-0.65638488 -0.10654814
-0.30719029 -2.18021761
0.55739344 -1.30501003 -1.41999234
1.52006190 -0.48909723 -0.72728670
1.52011770 -0.48914335
-0.30719789 -2.18022599 -0.71312140
0.55737433 -1.30494972
2.45551881
3.35376855
2.45549433
3.35375574
-1.01314941 -2.80654217 -1.25719373
0.51836429 -1.26771794 -2.50873918
0.44245383 -0.72028964
0.45843875
1.44768073
0.71877701
1.16112581
0.44244754
1.44223947
0.72023090
1.16312915
1.44788969 -1.16101124
1.44227748 -1.16312124
2.05192659
1.69647493
0.00018013
2.19305328
2.05296412
1.69471968
0.00002570
2.19529377
2.82506271
0.00033344
2.83509777
0.00005672
1.69692081 -2.19283968
1.69475586 -2.19526847
1.35643734
0.00002193
0.71207096
1.35817354
0.00000457
0.71315883
0.72591341
0.72728444
1.41778296
1.41560118
0.71254765
1.42000725
1.41830223
0.71398298
0.34703956
1.11280994
0.35007363
1.11238196
0.34695867 -1.41570433
1.11276712 -0.71274028
0.35007793 -1.41831842
1.11238318 -0.71401178
0.51307972 -1.26784979
-1.02578820 -2.79787265
4.06161515
2.50634340
1.25586005
1.24528703
0.51842626 -1.26772166
-1.01313565 -2.80650821
4.08376140
2.50875869
1.25726835
1.24695005
1.72662319
1.72232273

ACCE2P.T50E61D18M47ANUSCRI2P.T46305296
1
1
1
2.44932394
4.06153767
2.44920463
0.33686935
1.72656791 -1.24555227
0.33671538 -2.50622132
1
1
1
0.34076062
1.72230651 -1.24698994
0.34079412 -2.50900886
2.50899228
4.08375499
2.46299125
[(η5-C6H7)Ru(η6-C10H8)]+ + MeCN TS1
PBE/L2
E = -5282.238664 a.u.
ν = 82.19i cm–1
E0 = -5281.938476 a.u.
BPBE/L2
E = -5282.665424 a.u.
ν = 80.57i cm–1
E0 = -5282.365562 a.u.
ZPVE = 0.300188 a.u. = 188.3709 kcal/mol
T = 298.150 K: H = 200.6511 kcal/mol,
G = 157.4322 kcal/mol
ZPVE = 0.299862 a.u. = 188.1662 kcal/mol
T = 298.150 K: H = 200.4815 kcal/mol,
G = 157.2142 kcal/mol
6
6
6
6
6
6
1
1
1
1
1
1
1
44
6
6
6
6
6
6
6
6
6
6
1
1
1
1
1
1
1
1
7
6
6
1
1
1
-1.68077598 -1.23042382
0.59759496
1.14131989
6
6
6
6
6
6
1
1
1
1
1
1
1
44
6
6
6
6
6
6
6
6
6
6
1
1
1
1
1
1
1
1
7
6
6
1
1
1
-1.68973375 -1.22760408
0.57894896
1.12281122
-1.69888834
-1.80428042
1.02215952
1.42188548 -0.22667731
-1.70785051
-1.81811376
1.02849942
1.42895476 -0.24730795
-1.78510644 -0.96367991 -0.80250356
-1.92580559 0.39416419 -1.20278749
-2.33172970 -0.28102511
-3.43691131 -0.28515029
-1.79894096 -0.96147339 -0.82357244
-1.94376303 0.39868391 -1.22420328
-2.34293613 -0.27685232
-3.44847825 -0.28056965
1.58091817
1.56119880
1.56490527
1.54353769
-1.72113432
-1.94678088
2.46430609 -0.53324801
0.64934337 -2.26065495
-1.73972565
-1.97559508
2.47203548 -0.55398143
0.65346170 -2.28214774
-1.68727394 -1.75009515 -1.55051397
-2.02343133 -0.52583204
-1.47132929 -2.25829688
-1.70594782 -1.74896936 -1.57151394
-2.03632740 -0.52153375
-1.48139556 -2.25606343
2.60538613
0.90090843
1.88087019
0.05243201
1.84623389
0.24862434
2.59008467
0.88151566
1.86148542
0.02358542
1.82844332
0.23894866
-1.50396655
-0.07568944
1.18945087
1.80155722
0.10605080
0.41209228
-1.51398272
-0.08325631
1.17991005
1.80917645
0.11281562
0.41766687
1.71804036 -1.34141900
1.73505666 -1.33883302
2.63716844 -0.48183011 -0.46691714
2.62600784 0.90723981 -0.13157786
1.20052517 -0.96537775
2.69419593 -0.48819455 -0.44194333
2.68311934 0.90207063 -0.10619440
1.19096853 -0.96271563
1.51369900
0.89393416
1.49514623
0.88427101
1.69655894
3.47665587
4.33915537
1.33166453
1.79365718 -0.81606567
1.31066900 -1.79043933
1.71371142
3.57697162
4.48339151
1.33371436
1.78039624 -0.74905608
1.28625117 -1.68168242
3.49866207 -0.94532971 -1.47729220
4.35015024 -0.05798168 -2.12085122
0.76883327 -1.70178196
1.63805551 -2.38511757 -0.05916716
3.59883973 -0.96281130 -1.41151565
4.49431467 -0.08392866 -2.01256832
0.74918235 -1.69883958
1.65418438 -2.38168914 -0.07217644
2.18956620
2.16479045
1.59960340
0.74910525
5.02138122
3.46737239
2.39949206
0.75241482
1.99378422 -2.29730378
1.09588412
2.78203389
1.61591275
0.72934092
5.19666572
3.56882278
2.40229244
0.76036279
1.96202358 -2.15519851
1.08291844
2.75851181
2.85394544 -0.55948762
2.84120993 -0.49342766
5.04080075 -0.42418311 -2.88104013
3.50642027 -2.00590871 -1.73271695
5.21596551 -0.45831446 -2.73968669
3.60761870 -2.02337130 -1.66817247
0.62177750
1.09493612
1.68517508
2.31559151
0.89844733
2.30452988
0.73972475 -2.54863237
0.99204561 -3.57887069
1.30699790 -4.86472018
0.47465719 -5.20470829
1.48251736 -5.61067172
2.21021283 -4.78466623
0.64630676
1.01721412
1.48110583
2.09645666
0.62436227
2.08372983
0.73867665 -2.54088064
0.99990924 -3.61153025
1.32654577 -4.95022100
0.50752511 -5.34655843
1.48202887 -5.62014952
2.24461142 -4.92712528
[CpRu(η6-C10H8)]+ + MeCN TS1
PBE/L2
E = -5242.963459 a.u.
ν = 107.41i cm–1
E0 = -5242.691203 a.u.
BPBE/L2
E = -5243.371261 a.u.
ν = 104.19i cm–1
E0 = -5243.099365 a.u.
ZPVE = 0.272256 a.u. = 170.8430 kcal/mol
T = 298.150 K: H = 182.4572 kcal/mol,
G = 140.5142 kcal/mol
ZPVE = 0.271896 a.u. = 170.6175 kcal/mol
T = 298.150 K: H = 182.2801 kcal/mol,
G = 140.2889 kcal/mol
6
6
6
6
6
1
1
1
1
1
44
6
6
6
6
6
6
6
6
6
6
-1.80948543 -0.73517196
0.85221586
0.85717243
6
6
6
6
6
1
1
1
1
1
44
6
6
6
6
6
6
6
6
6
6
-1.81961675 -0.70755573
0.84220949
0.81427837
-1.83197359
-1.81208051
0.70950619
1.15330779 -0.50173666
-1.83916218
-1.81262303
0.73925271
1.15244695 -0.55589927
-1.80290605 -1.17597823 -0.51738055
-1.80846969 -0.01590692 -1.33670265
-1.80981629 -1.18106717 -0.51957566
-1.80892006 -0.03831510 -1.36655676
-1.82229911
-1.84804228 -1.37606787
2.18427924 -0.84090229
1.72924834
-1.82105166
-1.86628281 -1.32822611
2.17612013 -0.91748782
1.73346234
-1.75551583 -0.01437689 -2.42045123
-1.80339596 -2.20602159 -0.86079013
-1.75864439 -0.06298493 -2.45035193
-1.81371886 -2.21908298 -0.83927951
-1.87431057
1.34350771
1.73866195
-1.88461950
1.39368541
1.68081673
0.00175458 -0.00275946 -0.00181133
-0.00025623 -0.00064355 -0.02729301
1.20601526
0.27024583
1.79926999
0.17070440
1.19479657
0.26591875
1.78973694
0.17076223
1.78946079 -1.44755743
1.80368056 -1.45665294
2.68550981 -0.54722047 -0.52168512
2.66827372 0.83157305 -0.13641043
1.24148147 -1.10518218
2.73681211 -0.56567722 -0.49112152
2.72062816 0.81490671 -0.10538581
1.22763274 -1.11224771
1.42830298
0.89778366
1.41743921
0.89918784
1.73761233
3.51389718
4.37447120
1.22344272
1.74552453 -0.79357781
1.30251311 -1.78621637
1.75629068
3.60609574
4.50607362
1.21524274
1.71993623 -0.72643859
1.26475388 -1.68203421
3.54201195 -0.96647739 -1.55801846
4.38614631 -0.05347948 -2.17096911
3.63288131 -0.99684618 -1.49159711
4.51754612 -0.09318582 -2.06673302

ACCE2P.T07E19D36M67ANUSCRI0P.T76826763
1
1
1
1
1
1
1
1
7
6
6
1
1
1
0.79695080 -1.86282318
1.73312800 -2.48392722 -0.16429439
1.63686489
0.73344495
5.05552287
3.50117808
1
1
1
1
1
1
1
1
7
6
6
1
1
1
-1.86861835
1.74496225 -2.49229410 -0.16684417
2.05235416
2.28383974
0.57934972
2.00534993 -2.26714662
2.79536313 -0.49742867
1.13243830
2.73060091
1.65694812
0.70952496
5.21508364
3.59501462
2.27641017
0.57839633
1.95950386 -2.13405190
1.13205104
2.71358821
2.77044226 -0.43167826
5.07381554 -0.38783904 -2.94821502
3.55284416 -2.01681372 -1.85240200
5.23357372 -0.43635310 -2.81442954
3.64373685 -2.04706264 -1.78731820
0.71000371
1.12018840
1.63464960
2.01140233
0.84065117
2.45538990
0.85521892 -2.49165776
1.19952876 -3.52210013
1.63260874 -4.80603732
0.77103501 -5.37325831
2.11924411 -5.38823714
2.34761207 -4.66098971
0.74810960
1.04889982
1.42701064
1.76970227
0.56708872
2.23854132
0.85080846 -2.51132360
1.22663501 -3.56978945
1.69744290 -4.89249740
0.85576227 -5.50969707
2.17123470 -5.38552788
2.43336138 -4.81305853
[(η5-C6H7)Ru(η4-C10H8)(MeCN)]+ IM1
PBE/L2
BPBE/L2
E = -5282.245169 a.u.
E0 = -5281.944196 a.u.
E = -5282.670205 a.u.
E0 = -5282.369693 a.u.
ZPVE = 0.300973 a.u. = 188.8637 kcal/mol
T = 298.150 K: H = 201.3066 kcal/mol,
G = 158.5207 kcal/mol
ZPVE = 0.300512 a.u. = 188.5743 kcal/mol
T = 298.150 K: H = 201.1221 kcal/mol,
G = 157.6944 kcal/mol
6
6
6
6
6
6
1
1
1
1
1
1
1
44
6
6
6
6
6
6
6
6
6
6
1
1
1
1
1
1
1
1
7
6
6
1
1
1
-1.66531541 -1.26676062
0.67913312
1.19376502
6
6
6
6
6
6
1
1
1
1
1
1
1
44
6
6
6
6
6
6
6
6
6
6
1
1
1
1
1
1
1
1
7
6
6
1
1
1
-1.66848850 -1.26795154
0.66486366
1.18952427
-1.71233580
-1.98459160
0.99874052
1.37045960 -0.15206808
-1.71465647
-1.97765722
0.99797122
1.37738271 -0.15916021
-1.93552290 -1.03190197 -0.69799874
-2.15261903 0.31843116 -1.09995717
-2.23075823 -0.32334468
-3.32817955 -0.37241028
-1.92904504 -1.02632005 -0.71578898
-2.14512723 0.32807154 -1.11337513
-2.24513748 -0.32682643
-3.34461758 -0.37277118
1.72040495
1.83707812
1.70699927
1.80896219
-1.97625785
-2.29796388
2.40928482 -0.47961100
0.55488310 -2.15387210
-1.96827251
-2.28981412
2.41817957 -0.48158303
0.56899091 -2.16649008
-1.89099225 -1.82663703 -1.44158983
-1.78998311 -0.53741020
-1.37857654 -2.27873844
-1.88293416 -1.81853050 -1.46250420
-1.81790835 -0.54666513
-1.38747701 -2.28237129
2.70245224
0.96995452
1.89535815
2.69383335
0.95352404
1.89692177
-1.46207014
-0.15935684
1.17837980
1.79628174
0.13352568 -0.10381772
0.48879441
-1.47008944
-0.15085144
1.18748180
1.79240888
0.13496419 -0.10414308
0.48788554
1.61764763
0.01853087
1.62725812
0.03000618
1.72802818 -1.24337402
1.74852701 -1.24868855
2.78618542 -0.42450776 -0.57263522
2.75758240 0.95559223 -0.25134270
1.20784684 -0.89301285
2.81512856 -0.42938491 -0.55191793
2.78678465 0.95316340 -0.22910115
1.21608592 -0.89635028
1.29629175
0.63017662
1.30413262
0.64528562
1.67296780
3.70399192
4.68779333
1.38708833
1.82025159 -0.80831772
1.31501207 -1.66284255
1.69414840
3.75327835
4.75635992
1.38811935
1.81479371 -0.76419404
1.30335440 -1.59538711
3.76057853 -0.91643265 -1.44561780
4.71587304 -0.04757640 -1.98026473
0.80171952 -1.63559462
3.80955982 -0.92687986 -1.40424893
4.78440802 -0.06177710 -1.91405451
0.80692654 -1.63911452
1.98069062
1.98659078
1.64035631 -2.28197370 -0.30479271
1.66110625 -2.28722480 -0.29408354
1.54063454
0.74926589
5.43940651
3.68023780
2.45746202
0.83648236
1.98606565 -2.07935351
2.88359977 -0.56363425
0.79662314
2.55561765
1.56360523
0.75608586
5.52198950
3.73189132
2.45857824
0.83536067
1.97054431 -1.99316891
2.87812491 -0.51815796
0.81356090
2.56428936
5.48922107 -0.43563018 -2.64362813
3.78073662 -1.97853390 -1.69596992
5.57185920 -0.45366333 -2.55896390
3.83195921 -1.98926802 -1.65424303
0.51248395
0.95352415
1.53141195
1.23568612
1.19455560
2.62700312
0.61059589 -2.08326144
0.86143899 -3.12621760
1.17224769 -4.41456667
0.41870536 -5.15727582
2.16060345 -4.75587771
1.17777146 -4.32759943
0.52382030
0.90584684
1.39685708
1.06116068
1.02287826
2.49527512
0.61662262 -2.10681867
0.87101603 -3.17356738
1.18804142 -4.50130464
0.42861034 -5.22123399
2.17124461 -4.81938464
1.20983757 -4.49126519
[CpRu(η4-C10H8)(MeCN)]+ IM1
PBE/L2
BPBE/L2
E = -5242.979377 a.u.
E0 = -5242.706294 a.u.
E = -5243.385375 a.u.
E0 = -5243.112785 a.u.
ZPVE = 0.273082 a.u. = 171.3619 kcal/mol
T = 298.150 K: H = 183.1527 kcal/mol,
G = 140.9376 kcal/mol
ZPVE = 0.272589 a.u. = 171.0525 kcal/mol
T = 298.150 K: H = 182.9488 kcal/mol,
G = 140.8882 kcal/mol
6
6
6
6
6
1
1
1
1
1
-1.80866791 -0.74426156
1.01219523
1.00470356
6
6
6
6
6
1
1
1
1
1
-1.81490638 -0.45766438
1.15371898
0.78089807
-1.87548551
-2.04559337
0.68657601
1.12292813 -0.34893821
-1.90767984
-2.06786421
0.92852068
0.99362605 -0.63777265
-1.93705115 -1.20769072 -0.34371651
-2.09280834 -0.05770338 -1.17311745
-1.91379894 -1.25052507 -0.04250418
-2.07194846 -0.36028417 -1.14916333
-2.15414196
-1.70040710 -1.37263270
2.14998306 -0.68325271
1.89169411
-2.17045992
-1.71142686 -0.84027401
1.90250881 -1.22374854
2.16546692
-2.19396047 -0.07231100 -2.25475784
-1.93995013 -2.24206807 -0.67393657
-2.17712857 -0.65400793 -2.18966621
-1.88255130 -2.33533745 -0.09776379
-1.81368705
1.33370859
1.87538581
-1.87076231
1.77863926
1.45677085

ACCEPTED MANUSCR-I0P.T14778418
44
6
6
6
6
6
6
6
6
6
6
1
1
1
1
1
1
1
1
7
6
6
1
1
1
-0.14839628
1.24310491
0.05549048 -0.17527092
0.31378007 1.53478341
1.87962443 -1.35980821 -0.10950938
44
6
6
6
6
6
6
6
6
6
6
1
1
1
1
1
1
1
1
7
6
6
1
1
1
0.04551105 -0.18981903
0.16208124 1.53320702
1.26134682
1.88306720 -1.42104514 -0.21039994
2.92389670 -0.53161819 -0.69858175
2.92671871
2.90342153 -0.48821369 -0.65630849
2.88648588
0.87217752 -0.24158589
0.80312045 -0.19897742
1.26470958 -1.05487885
1.12204452
0.68990826
1.25859393 -1.17939666
1.03112417
0.75469244
1.84687495
3.82414443
4.78879367
1.26590321
1.88852711
3.89561600
4.87000940
3.88997341 -0.92306977 -1.63963124
4.86718717 -0.01609950 -2.05665834
0.78229192 -1.98376057
1.79549550 -2.41355912 -0.65546185
1.80525979
0.78737686
5.63812103
3.89682632
5.63309486 -0.33269042 -2.76558785
3.88676932 -1.94397471 -2.02608482
0.62527023
0.97829937
1.42441826
1.05402175
1.05333417
2.52288152
1.15723597
1.77014263 -0.76832708
1.32209171 -1.67086691
3.85843183 -0.91656241 -1.58726677
4.80568195 -0.01820539 -2.07930392
1.71263662 -0.65298856
1.29878371 -1.56443514
0.81377050 -1.83165572
1.73695348
1.58997293
1.80999425 -2.37989797 -0.49003544
1.74187875
0.76648997
5.53443936
3.80718976
2.32404547
0.60721702
0.93461263
2.46885478
2.19835477
0.40353976
1.07087389
2.48359819
2.01746709 -2.05689698
2.81519104 -0.45413282
2.00018641 -1.89225132
2.73635161 -0.27402796
5.56454784 -0.36242601 -2.78234274
3.86881708 -1.95903959 -1.91008605
0.62804285
1.03227965
1.55715635
1.23392437
1.20670255
2.65572921
0.63083070 -1.97079042
0.96055720 -3.00804960
1.37003343 -4.29123552
0.67468665 -5.07826641
2.38031001 -4.54412891
1.37474221 -4.25002914
0.70986235 -1.96977420
1.09724083 -3.00752075
1.57995371 -4.30049932
0.92414866 -5.10114519
2.59969547 -4.47580724
1.59181665 -4.33106973