Successive O-H and sp3 C-H bond activation of ortho-substituted phenols by a ruthenium(0) complex

Article abstract of DOI:10.1016/S0022-328X(00)00169-8

Successive O-H and sp³ C-H bond activation of ortho-substituted phenols has been achieved by the reactions of Ru(1,5-cyclooctadiene)(1,3,5-cyclooctatriene) (1) with 2,6-xylenol and 2-allylphenol in the presence of PMe₃ giving oxaruthenacycle complexes such as cis-Ru[OC₆H₃(2-CH₂)(6-Me)](PMe ₃)₄ (4) or Ru[OC₆H₄(2-η³-C₃H ₄)](PMe₃)₃ (5), respectively. They are formed by the initial protonation of Ru(1-2-η²:5-6-η ²-cycloocta-1,5-diene)(1-4-η ⁴-cycloocta-1,3,5-triene)(PMe₃) by phenols giving cationic (η⁵-cyclooctadienyl)ruthenium(II) complexes [Ru(η⁵-C₈H₁₁)(PMe₃) ₃]⁺[OAr]^-·(HOAr)_n [Ar = C₆H₃Me₂-2,6 (2a), C₆H₄(2-CH₂CH=CH₂) (2b), C₆H₄{2-(E)-CH-CHMe} (2c), Ph (2d); C₆H₄Me-2 (2e); C₆H₄(2-CHMe₂) (2f), and C₆H₄(2-CMe₃) (2g)] followed by sp³ C-H bond cleavage reaction. The molecular structure of 2c reveals that the cyclooctadienyl group coordinates to the ruthenium center by an η⁵-fashion, where one equivalent of (E)-2-propenylphenol is associated with aryloxo anion. Further treatment of 2a and 2c with PMe₃ results in the formation of oxaruthenacycle complexes to give 4 and 5, respectively. These facts clearly demonstrate that this sp³ C-H bond cleavage reaction occurs at a divalent ruthenium center. On the other hand, reactions of 2d-g afford (hydrido)(aryloxo)ruthenium(II) complexes, cis-Ru(H)(OAr)(PMe₃)₄ [Ar = Ph (6a), C₆H₄Me-2 (6b), C₆H₄(2-CHMe₂) (6c), C₆H₄(2-CMe₃) (6d)].

Full text of DOI:10.1016/S0022-328X(00)00169-8

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 607 (2000) 18–26
Successive OꢀH and sp3 CꢀH bond activation of ortho-substituted
phenols by a ruthenium(0) complex
Masafumi Hirano, Naoki Kurata, Sanshiro Komiya *
Department of Applied Chemistry, Faculty of Technology, Tokyo Uni6ersity of Agriculture and Technology, 2-24-16 Nakacho, Koganei,
Tokyo 184-8588, Japan
Received 26 January 2000; received in revised form 7 March 2000
This paper is dedicated to Professor Martin A. Bennett on his retirement from ANU and in honor of his tremendous contributions to
organometallic chemistry.
Abstract
Successive OꢀH and sp3 CꢀH bond activation of ortho-substituted phenols has been achieved by the reactions of Ru(1,5-cy-
clooctadiene)(1,3,5-cyclooctatriene) (1) with 2,6-xylenol and 2-allylphenol in the presence of PMe3 giving oxaruthenacycle
complexes such as cis-Ru[OC6H3(2-CH2)(6-Me)](PMe3)4 (4) or Ru[OC6H4(2-h3-C3H4)](PMe3)3 (5), respectively. They are formed
by the initial protonation of Ru(1-2-h2:5-6-h2-cycloocta-1,5-diene)(1-4-h4-cycloocta-1,3,5-triene)(PMe3) by phenols giving cationic
(h5-cyclooctadienyl)ruthenium(II) complexes [Ru(h5-C8H11)(PMe3)3]+[OAr]−·(HOAr)n [Ar=C6H3Me2-2,6 (2a), C6H4(2-
CH2CHꢁCH2) (2b), C6H4{2-(E)-CHꢁCHMe} (2c), Ph (2d); C6H4Me-2 (2e); C6H4(2-CHMe2) (2f), and C6H4(2-CMe3) (2g)]
followed by sp3 CꢀH bond cleavage reaction. The molecular structure of 2c reveals that the cyclooctadienyl group coordinates to
the ruthenium center by an h5-fashion, where one equivalent of (E)-2-propenylphenol is associated with aryloxo anion. Further
treatment of 2a and 2c with PMe3 results in the formation of oxaruthenacycle complexes to give 4 and 5, respectively. These facts
clearly demonstrate that this sp3 CꢀH bond cleavage reaction occurs at a divalent ruthenium center. On the other hand, reactions
of 2d–g afford (hydrido)(aryloxo)ruthenium(II) complexes, cis-Ru(H)(OAr)(PMe3)4 [Ar=Ph (6a), C6H4Me-2 (6b), C6H4(2-
CHMe2) (6c), C6H4(2-CMe3) (6d)]. © 2000 Elsevier Science S.A. All rights reserved.
Keywords: Oxaruthenacycle; Successive bond activation; CꢀH bond activation; Phenols; Ruthenium
CꢀH bond activation of triphenylphosphine ligand (or-
thometallation) [3] as well as metacrylates [4], aromatic
ketones [5], benzylalcohol [6], phenols [7] and pyridines
[8] suggests importance of prior coordination of sub-
strates to bring a CꢀH bond near the ruthenium center.
Our basic working hypothesis is that when an sp3 CꢀH
bond is forced to approach a ruthenium center, the
bond cleavage reaction should occur as illustrated in
Scheme 1.
1. Introduction
CꢀH bond activation of organic substrates by transi-
tion metal complexes has attracted a great deal of
interest for its potential synthetic applications [1]. Low
valent ruthenium complexes are particularly paid much
attention toward CꢀH bond activation since Chatt and
Davidson revealed oxidative addition of the CꢀH bond
of naphthalene to ruthenium(0) [2]. However, examples
for sp3 CꢀH bond activation is still very limited to date
in comparison with that for sp2 CꢀH bond. This may
be partly due to difficulty for the former bond in
approaching the metal center than the latter. Thus, sp2
However, activation of sp3 CꢀH bond based on this
strategy is still limited for late transition metal com-
* Corresponding author. Tel.: +81-42-388-7043; fax: +81-42-387-
7500.
E-mail address: komiya@cc.tuat.ac.jp (S. Komiya).
Scheme 1.
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(00)00169-8

M. Hirano et al. / Journal of Organometallic Chemistry 607 (2000) 18–26
19
plexes [9]. Published examples involve the sp3 CꢀH
bond activation of ortho substituted aryloxo ligands by
Group 6 metal complexes [10], ortho substituted phenyl
isocyanides by Ru(0) [11], and methyl groups in substi-
tuted phosphine [12] and amine ligands [13].
triplets at 0.45 ppm is assigned as the aliphatic endo-
proton H(7-endo) which is coupled to the three protons
at 1.26 [H(7-exo)] and 2.06 ppm [H(6-exo) and H(8-
exo)] with coincidentally the same coupling constant
and two protons at 1.75 ppm [H(6-endo) and H(8-
endo)]. The high-field shift of H(7-endo) is considered
to be caused by the shielding effect of the h5-cycloocta-
dienyl ligand. A triplet at 5.98 ppm is assigned to the
central dienyl proton H(3) that is coupled to the neigh-
boring dienyl protons [H(2) and H(4)] at 4.49 ppm. A
broad peak at 3.05 ppm is coupled to both dienyl [H(2)
and H(4)] and aliphatic protons [H(6) and H(8)] and is
therefore assigned to the outer dienyl protons [H(1) and
H(5)]. Two intensive broad singlets at 1.41 and 1.76
ppm are assigned as three PMe3 ligands. A sharp singlet
at 2.19 ppm, and two resonances in the aromatic region
at 6.32 (t) and 6.75 (d) ppm are assignable to the ortho
methyl, and para and meta protons, respectively. Detail
We have previously demonstrated successive CꢀO
and sp3 CꢀH bond activation of allyl 2,6-xylyl ether
giving an oxaruthenacycle complex with evolution of
propylene [14]. This reaction is considered to occur in a
stepwise manner by oxidative CꢀO bond addition to
ruthenium(0) giving the aryloxoruthenium(II) complex
followed by sp3 CꢀH bond cleavage of the ortho methyl
group. Reaction of a ruthenium(0) complex with ortho
substituted phenols giving aryloxoruthenium(II) is also
considered to be a promising route to sp3 CꢀH bond
activation, since phenols are know to react with ruthe-
nium to give (hydrido)(phenoxo)ruthenium complexes
[15]. Herein we wish to report the reaction of ortho
substituted phenols by Ru(1,5-cyclooctadiene)(1,3,5-cy-
clooctatriene) (1) in combination with PMe3, leading to
a facile protonation to the 1,3,5-cyclooctatriene ligand
followed by sp3 CꢀH bond activation of the ortho
methyl group. A part of this study has been reported as
a communication [14].
1
analysis of the H-NMR spectrum indicates that the
relative integration ratios of the signals due to the
aryloxo group always exceed the value expected, sug-
gesting presence of accompanying 2,6-xylenol in 2a.
However, the signal due to the OH hydrogen was not
observed. When one equivalent of 2,6-xylenol was
added to 2a at room temperature (r.t.), these signals of
the aryloxo moieties completely merged into the unique
set without significant broadening. These facts suggest
the occurrence of rapid exchange reaction between 2,6-
dimethylphenoxo anion and the associated 2,6-xylenol
in NMR time scale. Treatments of 1/PMe3 with 2-al-
lylphenol, phenol, ortho-cresol, 2-isopropylphenol, and
2. Results and discussion
2.1. Reaction of
Ru(1,5-cyclooctadiene)(1,3,5-cyclooctatriene) (1) with
phenols
2-tert-butylphenol
analogous (h5-cyclooctadienyl)ruthenium(II) complexes
[Ru(h5-C8H11)(PMe3)3]+[OAr]−·(HOAr)n
[Ar=
also
yielded
corresponding
Reaction of 1 with 2,6-xylenol in hexane in the
presence of PMe3 caused immediate deposition of white
powder of [Ru(h5-C8H11)(PMe3)3]+[OC6H3Me2-2,6]−
·[HOC6H3Me2-2,6] (2a) (Eq. (1)).
C6H3Me2-2,6 (2a), C6H4(2-CH2CHꢁCH2) (2b), C6H4{2-
(E)-CHꢁCHMe} (2c), Ph (2d); C6H4Me-2 (2e);
C6H4(2-CHMe2) (2f), and C6H4(2-CMe3) (2g)]. The co-
ordination mode of the h5-cyclooctadienyl ligand in
these complexes was unambiguously confirmed by X-
ray structure analysis of 2c (Fig. 1 and Table 1).
The overall structure of 2c is best regarded as three
legged chair form with counter anion. Bond distances
of RuꢀC(1), RuꢀC(2), RuꢀC(3), RuꢀC(4), and RuꢀC(5)
,
are in the range 2.17–2.31 A, suggesting the C8H11
moiety is coordinating to the Ru in an h5-fashion. The
aryloxo moiety is isomerized to (E)-propenylphenoxo
group locating far from the ruthenium center and is
associated with one molecule of (E)-2-propenylphenol,
indicating the ionic character of 2c. The orientation of
two aryloxo moieties and the bond length between two
(1)
1
1
The H-NMR resonances of 2a were assigned by H–
1H COSY as well as by comparison with the spectra of
related 1-5-h5-cyclooctatrienyl complexes such as Ru(1-
5-h5-C8H11)2 [16], Ru(1-5-h5-C8H11)(1-3-h3:5-6-h2-
C6H11) [16], [Ru(1-5-h5-C8H11)(PMe2Ph)3]+[BPh4]−
[17], and [Ru(1-5-h5-C8H11)(arene)]+[PF6]− [18]. The
1H–1H COSY of 2a revealed spin-correlated 11 protons
suggesting the presence of a C8H11 moiety. A quartet of
,
oxygen atoms (2.46 A) suggest hydrogen bonding be-
tween the aryloxo anion and 2-propenylphenol [19]. It
is interesting to note that while the allyl moiety re-
mained intact in the reaction of 1/PMe3 with 2-allylphe-
nol giving 2b at r.t., heating of the reaction mixture led
to 2c.

20
M. Hirano et al. / Journal of Organometallic Chemistry 607 (2000) 18–26
Fig. 1. Molecular structure of [Ru(h3-C8H11)(PMe3)3]+[OC6H4{2-(E)-CHꢁCHMe}]·[HOC6H4{2-(E)-CHꢁCHMe}] (2c). Ellipsoids represent 50%
probability. All hydrogen atoms are omitted for clarity.
Without exception, the reactions of 1/PMe3 with
phenols quantitatively liberated 1,5-cyclooctadiene (1,5-
COD) during the formation of 2. Therefore the origin
of the h5-cyclooctadienyl group is considered to be the
protonation of the 1,3,5-cyclooctatriene (1,3,5-COT)
ligand in 1. Actually, less protic alcohols or amine such
as 2,6-dimethylcyclohexanol, tert-butyl alcohol or 2,6-
dimethylaniline remained unreacted under these condi-
tions, but protonation of 1 by acid such as HBF4 is
reported [17]. Phenols having bulky substituents at the
ortho positions such as 2,6-diethylphenol, 2,6-di(iso-
propyl)phenol, or 2,6-di(tert-butyl)phenol also did not
cause the protonation of the 1,3,5-COT ligand but gave
fac-Ru(6-h1:1-3-h3-C8H10)(PMe3)3 (3), which is inde-
pendently prepared by the reaction of 1 with PMe3 [20].
(2)
Complex 4 was characterized by NMR, IR and ele-
1
mental analysis as well as chemical reactions. The H-
NMR spectrum of 4 shows a characteristic triplet of
triplets at 2.68 ppm with 2H integration ratio due to the
ortho methylene protons. This signal indicates that the
ortho methylene group is directly bonded to Ru and is
Table 1
,
Selected bond lengths (A) and angles (°) for 2c
2.2. Reaction of
[Ru(p5-C8H11)(PMe3)3]+[OAr]−·(HOAr)n (2)
Ru(1)ꢀP(1)
Ru(1)ꢀP(3)
Ru(1)ꢀC(2)
Ru(1)ꢀC(4)
O(1)ꢀO(2)
C(2)ꢀC(3)
C(4)ꢀC(5)
C(6)ꢀC(7)
C(8)ꢀC(1)
2.356(3)
2.353(3)
2.19(1)
2.17(1)
2.46(1)
1.45(2)
1.39(2)
1.44(2)
1.51(2)
Ru(1)ꢀP(2)
Ru(1)ꢀC(1)
Ru(1)ꢀC(3)
Ru(1)ꢀC(5)
C(1)ꢀC(2)
C(3)ꢀC(4)
C(5)ꢀC(6)
C(7)ꢀC(8)
2.317(3)
2.31(1)
2.23(1)
2.29(1)
1.38(2)
1.43(2)
1.52(2)
1.56(2)
Treatment of [Ru(h5-C8H11)(PMe3)3]+[OC6H3Me2-
2,6]−·(HOC6H3Me2-2,6) (2a) with PMe3 at 70°C for
15.5 h resulted in sp3 CꢀH bond cleavage of the ortho
methyl group in the aryloxo anion giving an ox-
aruthenacycle
¸¹¹¹¹¹¹¹º
complex
cis-Ru[OC6H3(2-CH2)(6-
Me)](PMe3)4 (4) in 69% yield with concomitant
formation of 1,3-COD and 2,6-xylenol. A small amount
of 3 was also formed in the reaction (vide infra). The
h5-C8H11 moiety is considered to act as the hydrogen
acceptor for the CꢀH bond activation liberating 1,3-
COD (Eq. (2)).
P(1)ꢀRu(1)ꢀP(2)
P(2)ꢀRu(1)ꢀP(3)
C(1)ꢀC(2)ꢀC(3)
C(3)ꢀC(4)ꢀC(5)
C(5)ꢀC(6)ꢀC(7)
C(1)ꢀC(8)ꢀC(7)
96.9(1)
93.1(1)
127(1)
129(1)
118(1)
114(1)
P(1)ꢀRu(1)ꢀP(3)
C(2)ꢀC(1)ꢀC(8)
C(2)ꢀC(3)ꢀC(4)
C(4)ꢀC(5)ꢀC(6)
C(6)ꢀC(7)ꢀC(8)
91.9(1)
125(1)
123(1)
123(1)
112(1)

M. Hirano et al. / Journal of Organometallic Chemistry 607 (2000) 18–26
21
afforded 2c and 2e, respectively. These data suggest that
3 is also susceptible to protonation giving (h5-cycloocta-
dienyl)ruthenium(II) (2). However, in all cases starting
from 3, the reaction giving 2 proceeded much slower
compared to those from 1/PMe3 (see Section 4). These
facts suggest that protonation of the COT ligand in
1/PMe3 is faster than protonolysis of the h1:h3-COT
ligand in 3.
coupled to two magnetically equivalent trans P nuclei
and two cis inequivalent P nuclei having coincidentally
similar coupling constants. The ortho methyl group
appears as a singlet at 2.53 ppm. The 31P{1H}-NMR
spectrum of 4 shows a typical AM2X pattern at ꢀ13.8
(td, J=24, 13 Hz, 1P), −0.96 (dd, J=32, 24 Hz, 2P),
and 10.7 ppm (td, J=32, 13 Hz, 1P), suggesting that the
PMe3 ligands occupy the sites trans to each other and
the residual two cis sites in an octahedral geometry.
Two triplet of doublets at −13.8 and 10.7 ppm are
assigned to the phosphorus nuclei trans to the methylene
and aryloxo groups, respectively, reflecting the stronger
trans influence by the alkyl ligand than the aryloxo
ligand [15,21]. Protonolysis of 4 with HCl or HCꢂCPh
led to quantitative liberation of 2,6-xylenol supporting
the oxaruthenacycle structure. Alternatively, 4 can also
be derived from the reaction of 1/PMe3 with allyl
2,6-xylyl ether [14].
2.4. Possible mechanism for successi6e OꢀH and sp3
CꢀH bond acti6ation
By taking present results into account, a possible
mechanism for these reactions is proposed as shown in
Scheme 2.
As established previously, treatment of 1 with PMe3
rapidly gives Ru(1-2-h2;5-6-h2-cod)(1-4-h4-cot)(PMe3)
(7) [23] but the formation of 3 is basically very slow [22].
Both 3 and 7 give (h5-cyclooctadienyl)ruthenium(II) 2
by the reaction with phenols, but the reaction of 3 is
much slower than that of 7. Therefore, 2 is probably
formed directly from 7 rather than 3. This process is
regarded as a protonation since less protic alcohols such
as 2,6-dimethylcyclohexanol remained unreacted. How-
ever, since bulky ortho substituents in phenols discour-
aged the formation of 2, this process may involve prior
protonation of phenols to Ru giving an intermediate
such as A. This process is reasonable, since such a
protonation process leading to the h5-cyclooctadienyl
intermediate B has been proposed by Tkachenko and
Chaudret [17]. The aryloxo group in B can be displaced
by PMe3 to give a thermodynamically stable cationic
complex 2. When 2,6-xylenol bearing methyl groups at
both ortho-positions is employed, one of the ortho
methyl group is forced to approach to the ruthenium
center in B, leading to sp3 CꢀH bond cleavage to give 4
with liberation of 1,3-COD [24]. When the 1,3,5-COT
ligand is simply liberated from A, (hydrido)(aryloxo)-
ruthenium(II) complexes are formed. It should be noted
that in these CꢀH bond activation, the presence of
hydrogen acceptor is very important [25]. 1,3,5-COT
acts as the hydrogen acceptor in the reaction of 2,6-
xylenol, whereas in the reaction of 2-allylphenol, the
reactant plays such role exclusively giving the hydro-
genated product (2-propylphenol). Without exception
no hydrogen evolution was observed in these reactions.
It is also worthwhile to note that the sp3 CꢀH bond
cleavage is clearly subsequent to the protonation and
thus occurs at a divalent ruthenium center in this
system. Facile approach of the ortho substituent would
induce the sp3 CꢀH bond activation.
Similar CꢀH bond activation took place by heating of
[Ru(h5-C8H11)(PMe3)3]+[OC6H4{2-(E)-CHꢁCH-
Me}]·[HOC6H4{2-(E)-CHꢁCHMe}] (2c) at 70°C giving
a
new oxaruthenacycle complex Ru[OC6H4(2-h3-
C3H4)](PMe3)3 (5), quantitatively. In this reaction 1,3,5-
COT, 1,3-COD and 2-propylphenol were detected in 96,
7 and 101% yields, respectively. These results indicate
that 2-propenylphenol acted as a hydrogen acceptor
instead for this CꢀH bond cleavage. The X-ray structure
of the PEt3 analogue of 4 has been reported in a
preliminary communication [14].
In contrast, reactions of 2d–g with PMe3 under
similar conditions did not lead to the CꢀH bond activa-
tion of aryloxo group, but produced (hydrido)-
(aryloxo)ruthenium(II) complexes cis-Ru(H)(OAr)-
(PMe3)4 [Ar=Ph (6a), C6H4Me-2 (6b), C6H4CHMe2-2
(6c), C6H4CMe3-2 (6d)] with liberation of 1,3,5-COT.
2.3. Reaction of fac-Ru(6-p1:1-3-p3-C8H10)(PMe3)3 (3)
with phenols
We previously reported formation of 3 by the reaction
of 1 with PMe3 in the absence of phenols [22]. Treat-
ment of 3 with 2,6-xylenol in the presence of PMe3
slowly but quantitatively gave 4 at 70°C for 10 days (Eq.
(3)).
(3)
The NMR study of the reaction mixture revealed
initial formation of 2a followed by quantitative conver-
sion to 4 after 326 h. No other intermediates were
observed during the reaction (see Section 4). Similarly,
treatments of 3 with 2-allylphenol and ortho-cresol also
3. Conclusions
In summary, we have succeeded in successive OꢀH
and sp3 CꢀH bond activation of ortho substituted phe-

22
M. Hirano et al. / Journal of Organometallic Chemistry 607 (2000) 18–26
Scheme 2.
nol by a ruthenium(0) complex. Bennett reported a
pioneering study on sp2 CꢀH bond cleavage of ancillary
phosphine ligand giving metallacycle complexes [26].
The present work demonstrates that sp3 CꢀH bond of
ortho substituted phenols can also be readily cleaved at
ruthenium. This study provides fundamental aspects for
sp3 CꢀH bond activation of organic molecules by a
low-valent ruthenium complex: (i) CꢀH bond should be
approach to the low-valent metal center; (ii) selection of
good hydrogen acceptor is also an important factor for
the CꢀH bond cleavage; (iii) thermodynamic stability of
the product may also be the driving force.
P(OPh)3 with MeMgI. Phenols were purchased from
Tokyo Chemical Industry or Aldrich and used as re-
ceived. Deuterated solvents for use in NMR experi-
ments were purchased from Kanto Chemical or Aldrich
and dried with sodium wire for C6D6 and CD3C6D5
and drierite for CD3COCD3, and were directly vacuum-
transferred into NMR. NMR spectra were recorded on
a JEOL LA-300 spectrometer (300.4 MHz for 1H, 121.6
MHz for 31P and 74.5 MHz for 13C) with chemical
1
shifts reported in ppm downfield from TMS for H and
13C, and from 85% H3PO4 in D2O. IR spectra were
recorded on a JASCO FTIR-410 spectrometer using
KBr disks. Elemental analyses were carried out using a
Perkin–Elmer 2400 series II CHN analyzer. Quantita-
tive analyses of evolved gases were performed by GLC
after collection of gases by using Toepler pump or by
internal standard method by GLC.
4. Experimental
4.1. General procedures
All manipulations were carried out under dry nitro-
gen using standard Schlenk and vacuum line techniques
unless otherwise noted. Benzene, toluene, hexane, 1,4-
dioxane and Et2O were dried over anhydrous calcium
chloride and then distilled from sodium benzophenone
ketyl under nitrogen. Ru(1,5-cyclooctadiene)(1,3,5-cy-
clooctatriene) (1) was prepared according to the litera-
ture method except for the magnetic stirring instead of
the ultrasonic irradiation during the reaction [16].
Ru(6-h1:1-3-h3-C8H10)(PMe3)3 was prepared as re-
ported previously [22,27]. PMe3 was prepared from
4.2. Preparation of
[Ru(p5-C8H11)(PMe3)3]+[OAr]−·(HOAr)n (2)
As a typical example, preparation of 2a by the reac-
tion of 1/PMe3 with 2,6-xylenol at r.t. is described in
detail. The other (h5-cyclooctadienyl)ruthenium com-
plexes 2b and 2d–g were prepared similarly and the
yields and NMR data are shown below. Complex 2c
was also prepared analogously but the reaction was
carried out at 70°C.

M. Hirano et al. / Journal of Organometallic Chemistry 607 (2000) 18–26
23
4.2.1. [Ru(p5-C8H11)(PMe3)3]+[OC6H3Me2-2,6]−·
(HOC6H3Me2-2,6) (2a)
CH2), 3.01 (br, 2H, 1- and 5-CH), 4.47 (m, 2H, 2- and
4-CH), 5.95 (t, J=6.4 Hz, 1H, 3-CH), 6.16 (dq, J=
16.1, 6.3 Hz, 2H, CHꢁCHMe), 6.31 (t, J=7.5 Hz, 2H,
OC6H4), 6.79 (td, J=7.5, 1.8 Hz, 2H, OC6H4), 6.91
(dq, J=16.1, 1.8 Hz, 2H,CHꢁCHMe), 6.92 (dd, J=
7.5, 1.8 Hz, 2H, OC6H4), 7.14 (dd, J=7.5, 1.8 Hz, 2H,
OC6H4). 31P{1H}-NMR (acetone-d6): l −5.99 (br,
PMe3). Anal. Calc. for C35H57O2P3Ru; C, 59.73; H,
8.16. Found: C, 60.55; H, 8.97%. The single crystals for
X-ray analysis were obtained from the dilute benzene
solution of 2c.
Complex 1 (332.8 mg, 1.055 mmol) was dissolved in
dry hexane (3 ml) and PMe3 (328 ml, 3.21 mmol) was
added into the solution. Immediately after addition of
2,6-xylenol (515.7 mg, 4.221 mmol) into the solution at
r.t., white powder was deposited. After stirring the
suspension for 3 h, the solution was removed and the
resulting white solid was washed with Et2O (15 ml×7)
and then dried in vacuo to give 2a. Yield, 322.5 mg
(0.443 mmol, 42%). Complete purification of cationic
complex 2a was unsuccessful because of incorporation
of 2,6-xylenol. Attempted recrystallization gave oily
materials also including hydrogen bonded 2,6-xylenol.
The amount of included 2,6-xylenol varied 1–2 mol per
2a. Therefore, only spectroscopic data are shown be-
low. 1H-NMR (acetone-d6): l 0.45 (qt, J=13.8, 2.7 Hz,
1H, endo-7-CH2), 1.26 (m, 1H, exo-7-CH2), 1.41 (m,
18Hz, PMe3), 1.75 (br, 2H, endo-6- and endo-8-CH2),
1.76 (m, 9H, PMe3), 2.06 (br, 2H, exo-6- and exo-8-
CH2), 2.19 (s, 14.4H, OC6H3Me2,), 3.05 (br, 2H, 1- and
5-CH), 4.49 (m, 2H, 2- and 4-CH), 5.98 (t, J=6.3 Hz,
1H, 3-CH), 6.32 (t, J=7.2 Hz, 2.8H, para-OC6H3),
6.75 (d, J=7.2 Hz, 5.6H, meta-OC6H3). 31P{1H}-NMR
(acetone-d6): l −5.95 (br, PMe3).
4.2.4. [Ru(p5-C8H11)(PMe3)3]+[OPh]−·(HOPh) (2d)
Reaction of 1 (112.7 mg, 0.357 mmol)/PMe3 (125 ml,
1.07 mmol) with phenol (140.2 mg, 1.49 mmol) gave 2d.
Yield, 186.0 mg (0.277 mmol, 78%). 1H-NMR (acetone-
d6): l 0.45 (qt, 1H, J=13.8, 2.7 Hz, 1H, endo-7-CH2),
1.26 (m, 1H, exo-7-CH2), 1.41 (br, 18 H, PMe3), 1.71
(m, 2H, endo-6- and endo-8-CH2), 1.76 (m, 9H, PMe3),
2.11 (br, 2H, exo-6- and exo-8-CH2), 3.06 (br, 2H, 1-
and 5-CH), 4.49 (m, 2H, 2- and 4-CH), 5.99 (t, J=6.3
Hz, 1H, 3-CH), 6.47 (t, J=7.5 Hz, 2.5 H, para-OPh),
6.82 (t, J=7.5 Hz, 5 H, ortho-OPh), 6.98 (t, J=7.5
Hz, 5 H, meta-OPh). 31P{1H}-NMR (acetone-d6): l
−5.94 (br, PMe3).
4.2.2. [Ru(p5-C8H11)(PMe3)3]+[OC6H4-
4.2.5. [Ru(p5-C8H11)(PMe3)3]+[OC6H4Me-2]−·
[HOC6H4(2-Me)] (2e)
(2-CH2CHꢁCH2)]−·{HOC6H4(2-CH2CHꢁCH2)} (2b)
Reaction of 1 (215.4 mg, 0.683 mmol)/PMe3 (212 ml,
2.05 mmol) with 2-allylphenol (375 ml, 2.73 mmol) gave
2b. Yield, 492.4 mg (0.617 mmol, 90%). 1H-NMR
(acetone-d6): l 0.45 (qt, 1H, J=13.8, 2.7 Hz, 1H,
endo-7-CH2), 1.26 (m, 1H, exo-7-CH2), 1.39 (br, 18 H,
PMe3), 1.67 (m, 2H, endo-6- and endo-8-CH2), 1.75 (m,
9H, PMe3), 2.11 (br, 2H, exo-6- and exo-8-CH2), 3.05
(br, 2H, 1- and 5-CH), 3.39 (d, J=6.3 Hz, 5.4 H,
CH2CHꢁCH2), 4.47 (m, 2H, 2- and 4-CH), 4.90 (d,
J=9.9 Hz, 2.7 H, CH2CHꢁCH2), 5.02 (d, J=16.5 Hz,
2.7 H, CH2CHꢁCH2), 5.97 (t, J=6.5 Hz, 1H, 3-CH),
6.08 (ddt, J=16.5, 9.9, 6.3 Hz, 2.7 H, CH2CHꢁCH2),
6.43 (t, J=7.5 Hz, 2.7 H, OC6H4), 6.84 (t, J=7.5 Hz,
2.7 H, OC6H4), 6.90 (d, J=7.5 Hz, 2.7 H, OC6H4),6.98
(d, J=7.5 Hz, 2.7 H, OC6H4). 31P{1H}-NMR (acetone-
d6): l −5.99 (br, PMe3).
Reaction of 1 (149.8 mg, 0.475 mmol)/PMe3 (170 ml,
1.46 mmol) with ortho-cresol (203.0 mg, 1.877 mmol)
1
gave 2e. Yield, 293.6 mg (0.416 mmol, 88%). H-NMR
(acetone-d6): l 0.45 (qt, 1H, J=13.8, 2.7 Hz, 1H,
endo-7-CH2), 1.26 (m, 1H, exo-7-CH2), 1.41 (br, 18 H,
PMe3), 1.71 (m, 2H, endo-6- and endo-8-CH2), 1.76 (m,
9H, PMe3), 2.11 (br, 2H, exo-6- and exo-8-CH2), 2.15
(s, 4.5 H, OC6H4Me), 3.05 (br, 2H, 1- and 5-CH), 4.48
(m, 2H, 2- and 4-CH), 5.98 (t, J=6.3 Hz, 1H, 3-CH),
6.40 (td, J=7.6, 1.2 Hz, 2.5 H, para-OC6H4), 6.82
(dd, J=7.6, 1.5 Hz, 2.5 H, ortho-OC6H4), 6.91 (dd,
J=7.6, 1.2 Hz, 2.5 H, meta-OC6H4), 6.93 (dd, J=7.6,
1.5 Hz, 2H, meta-OC6H4). 31P{1H}-NMR (acetone-d6):
l −5.96 (br, PMe3).
4.2.6. [Ru(p5-C8H11)(PMe3)3]+[OC6H4(2-CHMe2)]−·
[HOC6H4(2-CHMe2)] (2f)
4.2.3. [Ru(p5-C8H11)(PMe3)3]+[OC6H4{2-
Reaction of 1 (211.9 mg, 0.672 mmol)/PMe3 (240 ml,
(E)-CHꢁCHMe}]−·[HOC6H4{2-(E)-CHꢁCHMe}] (2c)
2-Allylphenol (260 ml, 1.99 mmol) was added to a
benzene solution (3 ml) of 1 (310.9 mg, 0.986 mmol)
with PMe3 (390 ml, 3.01 mmol) and the reaction mixture
was heated at 70°C for 3 days. Yield, 22.0 mg (0.0313
mmol, 3%). 1H-NMR (acetone-d6): l 0.44 (qt, 1H,
J=13.8, 2.7 Hz, 1H, endo-7-CH2), 1.29 (m, 1H, exo-7-
CH2), 1.37 (br, 18 H, PMe3), 1.69 (m, 2H, endo-6- and
endo-8-CH2), 1.73 (m, 9H, PMe3), 1.80 (dd, J=6.3, 1.8
Hz, 6H, CHꢁCHMe), 2.10 (br, 2H, exo-6- and exo-8-
2.06 mmol) with 2-isopropylphenol (360 ml, 2.68 mmol)
1
gave 2f. Yield, 361.8 mg (0.483 mmol, 72%). H-NMR
(acetone-d6): l 0.45 (qt, 1H, J=13.8, 2.7 Hz, 1H,
endo-7-CH2), 1.17 (d, J=7 Hz, 13.8 H, CHMe2), 1.26
(m, 1H, exo-7-CH2), 1.41 (br, 18 H, PMe3), 1.72 (m,
2H, endo-6- and endo-8-CH2), 1.76 (m, 9H, PMe3), 2.11
(br, 2H, exo-6- and exo-8-CH2), 3.06 (br, 2H, 1- and
5-CH), 3.20 (sep, J=7 Hz, 2.3 H, CHMe2), 4.50 (m,
2H, 2- and 4-CH), 6.00 (t, J=6.3 Hz, 1H, 3-CH), 6.36
(td, J=7.8, 1.2 Hz, 2.3 H, para-OC6H4), 6.76 (td,

24
M. Hirano et al. / Journal of Organometallic Chemistry 607 (2000) 18–26
¸¹¹¹¹¹¹¹¹¹º
J=7.8, 1.8 Hz, 2.3 H, ortho-OC6H4), 6.93 (dd, J=7.8,
1.8 Hz, 2.3 H, meta-OC6H4), 6.96 (dd, J=7.8, 1.2 Hz,
2.3 H, meta-OC6H4). 31P{1H}-NMR (acetone-d6): l
−5.95 (br, PMe3).
4.4. Preparation of fac-Ru[OC6H4(2-p3-C3H4)](PMe3)3
(5)
Complex 5 was prepared by the reaction of 3 (137.2
mg, 0.315 mmol) with 2-allylphenol (82 ml, 0.628 mmol)
in benzene at 70°C for 65 h. Yield, 37.4 mg (0.0810
mmol, 26%). This complex was also prepared by the
reaction of 1/PMe3 with 2-allylphenol in a similar way
to 4. 1H-NMR (C6D6): l 0.53 (d, J=8.1 Hz, 9 H,
PMe3), 1.09 (d, J=7.2 Hz, 9 H, PMe3), 1.26 (d, J=7.5
Hz, 9 H, PMe3), 1.91 (dd, J=12.3, 4.5 Hz, 1H, anti-
C3H4), 2.95 (m, 1H, syn-C3H4), 4.20 (dq, J=12.3, 7.5
Hz, 1H, central-C3H4), 4.89 (dt, J=7.5, 3.6 Hz, 1H,
syn-C3H4), 6.66 (t, J=7.3 Hz, 1H, OC6H4), 6.85 (d,
J=8.1 Hz, 1H, OC6H4), 7.15 (ddd, J=8.1, 7.3, 1.8 Hz,
1H, overlapped with residual benzene in C6D6), 7.24
(dd, J=7.3, 1.8 Hz, 1H, OC6H4). 31P{1H}-NMR
(C6D6): l -11.4 (t, J=25 Hz, 1P, PMe3), −0.49 (dd,
J=25, 16 Hz, 1P, PMe3), −0.39 (dd, J=25, 16 Hz,
1P, PMe3). Anal. Calc. for C18H35OP3Ru: C, 46.85; H,
7.64. Found: C, 46.75; H, 7.63%.
4.2.7. [Ru(p5-C8H11)(PMe3)3]+[OC6H4(2-CMe3)]−·
[HOC6H4(2-CMe3)] (2g)
Reaction of 1 (189.0 mg, 0.599 mmol)/PMe3 (180 ml,
1.54 mmol) with 2-tert-butylphenol (370 ml, 2.41 mmol)
1
gave 2g. Yield, 280.5 mg (0.340 mmol, 57%). H-NMR
(acetone-d6): l 0.45 (qt, 1H, J=13.5, 2.7 Hz, 1H,
endo-7-CH2), 1.26 (m, 1H, exo-7-CH2), 1.41 (br, 18 H,
PMe3), 1.43 (s, 23H, CMe3), 1.72 (br, 2H, endo-6- and
endo-8-CH2), 1.76 (m, 9H, PMe3), 2.11 (br, 2H, exo-6-
and exo-8-CH2), 3.05 (br, 2H, 1- and 5-CH), 4.49 (m,
2H, 2- and 4-CH), 5.98 (t, J=6.3 Hz, 1H, 3-CH), 6.36
(td, J=7.7, 1.3 Hz, 2.6H, para-OC6H4), 6.79 (td, J=
7.8, 1.8 Hz, 2.6H, ortho-OC6H4), 6.97 (dd, J=7.7, 1.3
Hz, 2.6H, meta-OC6H4), 7.02 (dd, J=7.7, 18 Hz, 2.6H,
meta-OC6H4). 31P{1H}-NMR (acetone-d6): l -5.95 (br,
PMe3).
¸¹¹¹¹¹¹¹º
4.3. Preparation of cis-Ru[OC6H3(2-CH2)(6-Me)]-
4.5. Preparation of cis-Ru(H)(OAr)(PMe3)4 (6)
(PMe3)4 (4)
As a typical example, preparation of 6a is described.
PMe3 (430 ml, 3.32 mmol) and 2,6-xylenol (134.4 mg,
1.10 mmol) were added into a benzene solution (5 ml)
of 1 (346.5 mg, 1.10 mmol) in this order. The pale
yellow solution was stirred at 70°C for 200 h. After
removal of all volatile materials under reduced pres-
sure, the resulting white solid was extracted with Et2O
(15 ml). The extract was evaporated to dryness and the
resulting white powder was recrystallized from pentane
at −30°C to yield white needles of cis-Ru[OC6H4(2-
CH2)(6-Me)](PMe3)4 (4). Yield, 143.5 mg (0.272 mmol,
25%). 1H-NMR (C6D6): l 0.90 (d, J=7.2 Hz, 9H,
apical-PMe3), 1.00 (t, J=2.9 Hz, 18H, equatorial-
PMe3), 1.17 (d, J=5.7 Hz, 9H, equatorial-PMe3), 2.53
(s, 3H, 6-Me), 2.68 (tt, J=14.3, 3.5 Hz, 2H, 2-CH2),
6.7–6.9, 7.1–7.2 and 7.4–7.5 (m, C6H3, overlapped
with C6D5H). 31P{1H}-NMR (C6D6): l −13.8 (td,
J=24, 13 Hz, 1P, PMe3 trans to CH2), −0.96 (dd,
J=32, 24 Hz, 2P, mutually trans PMe3), 10.7 (td,
J=32, 13 Hz, 1P, PMe3 trans to O). 13C{1H}-NMR
(C6D6): l 17.8 (s, C6H3(6-Me)), 17.9 (td, J=11, 3 Hz,
PMe3), 22.4 (d, J=14 Hz, PMe3), 23.2 (dq, J=54, 10
Hz, RuꢀCH2ꢀ), 24.7 (d, J=24 Hz, PMe3), 112.2 (s,
para-OC6H3), 124.5 (s, ortho-OC6H3), 126.0 (s, meta-
OC6H3), 129.4 (s, meta%-OC6H3), 138.4 (s, 6-OC6H3),
173.2 (s, ipso-OC6H3); these assignments were con-
firmed by 13C-1H shift correlation spectroscopy. IR
(KBr, cm−1): 2969 (w, wCH), 2908 (m, wCH), 1575 (m),
1466 (m), 1451 (m), 1422 (s), 1404 (sh), 1299 (s), 1273
(s), 1061 (w), 938 (vs), 850 (m), 842 (m), 739 (m), 709
(m), 625 (m), 526 (w). Anal. Calc. for C20H44OP4Ru: C,
45.71; H, 8.44. Found: C, 45.90; H, 8.50%.
Complexes 6b–d were also prepared in a similar way to
6a.
4.5.1. cis-Ru(H)(OPh)(PMe3)4 (6a)
Complex 1 (417.2 mg, 1.32 mmol) and phenol (133.8
mg, 1.422 mmol) were placed into a Schlenk tube to
which benzene (3 ml) was transferred under vacuum.
Into the reaction mixture PMe3 (690 ml, 5.33 mmol) was
added by a hypodermic syringe to start the reaction and
the mixture was stirred at 70°C for 160 h. All volatile
matters were removed and recrystallization of the re-
sulting white solid from hexane gave white microcrys-
tals of 6a. Yield, 100.0 mg (0.200 mmol, 15%). This
complex was characterized by comparison with the
literature data [15a].
4.5.2. cis-Ru(H)(OC6H4Me-2)(PMe3)4 (6b)
Reaction of 1 (191.8 mg, 0.6080 mmol)/PMe3 (325 ml,
2.51 mmol) with ortho-cresol (86.3 mg, 0.798 mmol)
1
gave 6b. Yield, 76.2 mg (0.148 mmol, 24%). H-NMR
(C6D6): l −7.55 (dq, J=102, 27 Hz, 1H, RuꢀH), 0.99
(d, J=7.2 Hz, 9H, PMe3), 1.15 (virtual t, J=2.8 Hz,
18H,PMe3), 1.17 (d, J=5.4 Hz, 9H, PMe3), 2.49 (s,
3H, 2-Me), 6.71 (t, J=6.6 Hz, 1H, OC6H4), 7.38 (d,
J=6.6 Hz, 1H, OC6H4), 7.44 (t, J=8.1 Hz, 1H,
OC6H4), 7.65 (d, J=8.1 Hz, 1H, OC6H4). 31P{1H}-
NMR (121.6 MHz, C6D6): l −11.6 (td, J=27, 16 Hz,
1P, PMe3), 1.17 (dd, J=33, 27 Hz, 2P, PMe3), 15.2
(td, J=33, 16 Hz, 1P, PMe3). IR (KBr, cm−1): 1858
(wRuꢀH). Anal. Calc. for C19H44OP4Ru: C, 44.44; H,
8.64. Found: C, 45.13; 8.86%.

M. Hirano et al. / Journal of Organometallic Chemistry 607 (2000) 18–26
25
4.5.3. cis-Ru(H)[OC6H4(2-CHMe2)](PMe3)4 (6c)
Reaction of 1 (115.2 mg, 0.365 mmol)/PMe3 (170 ml,
1.46 mmol) with 2-isopropylphenol (59 ml, 0.44 mmol)
gave 6e. Yield, 29.6 mg (0.0544 mmol, 15%). 1H-NMR
(C6D6): l −7.58 (dq, J=103, 27 Hz, 1H, RuꢀH), 0.98
(d, J=7.2 Hz, 9H, PMe3), 1.16 (virtual t, J=3.0 Hz,
18H, PMe3), 1.18 (d, J=5.4 Hz, 9H, PMe3), 1.49 (d,
J=7.0 Hz, 6H, CHMe2), 3.80 (sep, J=7.0 Hz, 1H,
CHMe2), 6.77 (t, J=7.7 Hz, 1H, OC6H4), 7.39 (d,
J=7.7 Hz, 1H, OC6H4), 7.40 (t, J=7.7 Hz, 1H,
OC6H4), 7.70 (d, J=7.7 Hz, 1H, OC6H4). 31P{1H}-
NMR (C6D6): l −12.5 (td, J=27, 17 Hz, 1P, PMe3),
1.34 (dd, J=33, 27 Hz, 2P, PMe3), 15.3 (td, J=33, 17
Hz, 1P, PMe3). IR (KBr, cm−1): 1873 (wRuꢀH). Anal.
Calc. for C21H48OP4Ru: C, 46.57; H, 8.93. Found: C,
46.39; H, 8.69%.
4.7.3. Reaction of 3 with ortho-cresol
Complex 3 (167.7 mg, 0.385 mmol) and ortho-cresol
(71.7 mg, 0.663 mmol) were dissolved in benzene (3 ml)
and PMe3 (62 ml, 0.60 mmol) was added into the
solution. The reaction mixture was stirred at 70°C for
72 h. After removal of all volatile matters, resulting
yellow oil was crystallized from a mixture of THF (1
ml) and hexane (1 ml) to give white cubes of 6b. Yield,
57.3 mg (0.112 mmol, 29%).
4.8. Acidolysis of 4 by HCl
Complex 4 (18.3 mg, 0.035 mmol) was placed in an
NMR tube and benzene-d6 (600 ml) was transferred into
the NMR tube under vacuum. Into the benzene-d6
solution of 4 were added 1,4-dioxane (2.0 ml, 0.023
mmol) as an internal standard (1,4-dioxane) and 6 M
4.6. Reaction of [Ru(p5-C8H11)(PMe3)3]+[OAr](HOAr)n
(2) with PMe3
HCl (20 ml, 0.13 mmol). The H-NMR showed forma-
1
tion of 2,6-xylenol (93%, 0.028 mmol).
The following reactions were carried out in an NMR
tube in benzene-d6 at 70°C in the presence of an inter-
nal standard (1,4-dioxane) and the yields of products
are described below.
4.9. Protonolysis of 4 by phenylacetylene
Complex 4 (9.1 mg, 0.017 mmol) was placed in an
NMR tube and benzene-d6 (600 ml) was transferred into
the NMR tube under vacuum. Into the solution were
added 1,4-dioxane (2.0 ml, 0.023 mmol) as an internal
standard and phenylacetylene (6.0 ml, 0.055 mmol) by a
hypodermic syringe. The 1H-NMR spectrum showed
formation of 2,6-xylenol (100%, 0.017 mmol).
Reaction of [Ru(h5-C8H11)(PMe3)3]+[OC6H3Me2-
2,6]−·(HOC6H3Me2-2,6) (2a) (4.7 mg, 0.0065 mmol)
with PMe3 (1.0 ml, 0.0097 mmol) at 70°C for 15.5 h
gave Ru[OC6H3(2-CH2)(6-Me)](PMe3)4 (4) (69%), 1,3-
COD (69%), 2,6-xylenol (293%) and 3 (30%).
Heating of [Ru(h5-C8H11)(PMe3)3]+[OC6H4{2-(E)-
CHꢁCHMe}]−·[H OC6H4{2-(E)-CHꢁCHMe}] (2c) (3.0
mg, 0.0043 mmol) at 70°C for 17 h gave Ru[OC6H4(2-
h3-C3H4)](PMe3)3 (5) (100%), 1,3-COD (7%), 2-propy-
lphenol (101%), and 1,3,5-COT (96%).
4.10. X-ray structure analysis of 2c
Complex 3 (97.3 mg, 0.223 mmol) was dissolved into
a benzene solution (2 ml) and then 2-allylphenol (30 ml,
0.23 mmol) was added into the solution. The reaction
mixture was stirred at 70°C for 65 h. All volatile
materials were removed from the mixture to give a light
yellow solid. Recrystallization of the solid from cold
Et2O (ca. 3 ml) gave a white precipitate, while complex
5 was obtained from the mother liquor in 11% yield
(11.3 mg, 0.0245 mmol). Recrystallization the white
precipitate from cold benzene gave clear light yellow
cubes of 2c. Yield, 76.2 mg (0.108 mmol, 48%).
Reaction of [Ru(h5-C8H11)(PMe3)3]+[OC6H4Me-2]−
·(HOC6H4Me-2) (2e) (8.9 mg, 0.012 mmol) with PMe3
(4.0 ml, 0.039 mmol) at 70°C for 10 h: cis-
Ru(H)(OC6H4Me-2)(PMe3)4 (6b) (71%), ortho-cresol
(210%), and 1,3,5-COT (46%).
4.7. Reaction of fac-Ru(6-p1:1-3-p3-C8H10)(PMe3)3 (3)
with phenols
4.7.1. Reaction of 3 with 2,6-xylenol
A Rigaku AFC-5R diffractometer with graphite-
,
A mixture of 3 (8.6 mg, 0.020 mmol) and 2,6-
dimethylphenol (2.8 mg, 0.023 mmol) were dissolved in
C6D6 (600 ml). After addition of PMe3 (5.0 ml, 0.05
mmol) by hypodermic syringe, the reaction mixture was
heated at 70°C for 10 days to give 4 (91%) and 1,3-
COD (90%).
monochromated MoꢀKa radiation (u=0.71069 A) was
used for data collection. A selected crystal of 2c was
mounted in glass capillaries (GLAS, 0.7 mmf) under
argon atmosphere. The collected data were solved by
Patterson methods, and refined by a full-matrix least-
square procedure using TEXSAN programs [28]. The
reflections with ꢀFoꢀ\3|ꢀFoꢀ were used in the refine-
ments. All non-hydrogen atoms except C(13) and
C(18)–C(21) were refined with anisotropic displacement
parameters. Hydrogen atoms were placed in calculated
positions and were not refined. Crystallographic data
for 2c is as follows: light yellow cube with crystal
4.7.2. Reaction of 3 with 2-allylphenol
Reaction of 3 (15.1 mg, 0.0347 mmol) with 2-al-
lylphenol (18 ml. 0.151 mmol) after 215 h in C6D6 (600
ml) at 70°C gave 5 (54%), 1,3,5-COT (38%), 2-propyl-
phenol (48%), and 1,3-COD (9%).

26
M. Hirano et al. / Journal of Organometallic Chemistry 607 (2000) 18–26
[6] F. Ozawa, I. Yamagami, A. Yamamoto, J. Organomet. Chem.
473 (1994) 265.
dimensions of 0.92×0.45×0.30 mm; C26H46OP3Ru·
,
C9H11O; a=19.423(6), b=23.974(8), c=16.099(8) A,
[7] (a) L.N. Lewis, J.F. Smith, J. Am. Chem. Soc. 108 (1986) 2728.
(b) J.F. Hartwig, R.G. Bergman, R.A. Andersen, J. Organomet.
Chem. 394 (1990) 417. (b) N. Bag, S. Bhanja Choudhury, A.
Paramanik, G. Kumar Lahiri, A. Chakravorty, Inorg. Chem. 29
(1990) 5013. (c) J.F. Hartwig, R.G. Bergman, R.A. Andersen, J.
Am. Chem. Soc. 113 (1991) 3404. (d) J.F. Hartwig, R.G.
Bergman, R.A. Andersen, J. Am. Chem. Soc. 113 (1991) 6499.
[8] E.J. Moore, W.R. Pretzer, T.J. O’Connell, J. Harris, L.
LaBounty, L. Chou, S. Grimer, J. Am. Chem. Soc. 114 (1992)
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[9] CꢀH bond activation of ortho substituents are carried out by
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3
,
,
V=7496(4) A ; MoꢀKa : u=0.71069 A; orthorhombic;
Pbca (no. 61); Z=8; Rigaku AFC-5R diffractometer;
collection method: ꢀ–2q ; reflections collected: 8428;
2q limit=54.9°; empirical ƒ-scan absorption correction
was applied; R=0.073; Rw=0.097.
5. Supplementary material
Tables of complete crystallographic data, bond
lengths, bond angles, anisotropic thermal parameters,
and final atomic coordinates have been deposited with
the Cambridge Crystallographic Data Centre, CCDC
139412. Copies of this information may be obtained
free of charge from: The Director, CCDC, 12 Union
Road, Cambridge, CB2 1EZ, UK (Fax: +44-1223-336-
033; e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).
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Acknowledgements
This work was financially supported by Proposal-
Based New Industry Creative Type Technology R&D
Promotion Program from the New Energy and Indus-
trial Technology Development Organization of Japan
(NEDO) and a Grant-in-Aid for Scientific Research
from the Ministry of Education, Science, Sports and
Culture, Japan.
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