Synthesis of RuCl2(xantphos)L (L = PPh3, P(OPh)3, DMSO) complexes, and their catalytic activity for the addition of carboxylic acids onto olefins

Article abstract of DOI:10.1016/j.jorganchem.2015.04.016

Abstract Readily synthesis of a series of RuCl₂(xantphos)L (L = PPh₃, P(OPh)₃, DMSO) was achieved. Thus, RuCl₂(xantphos)PPh₃ was synthesised by the reaction of RuCl₂(PPh₃)_3<

Full text of DOI:10.1016/j.jorganchem.2015.04.016

Accepted Manuscript
Synthesis of RuCl (xantphos)L (L = PPh , P(OPh) , DMSO) Complexes, and their
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Catalytic Activity for the Addition of Carboxylic Acids onto Olefins
Shoko Higashi, Hiroto Takenaka, Yoshihiko Ito, Yohei Oe, Tetsuo Ohta
PII:
S0022-328X(15)00217-X
10.1016/j.jorganchem.2015.04.016
JOM 19002
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 21 November 2014
Revised Date: 4 March 2015
Accepted Date: 6 April 2015
Please cite this article as: S. Higashi, H. Takenaka, Y. Ito, Y. Oe T. Ohta, Synthesis of
RuCl (xantphos)L (L = PPh , P(OPh) , DMSO) Complexes, and their Catalytic Activity for the
2
3
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Addition of Carboxylic Acids onto Olefins, Journal of Organometallic Chemistry (2015), doi: 10.1016/
j.jorganchem.2015.04.016.
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Graphical Abstract Synopsis
RuCl2(xantphos)(PPh3) was readily synthesized from RuCl2(PPh3)3 in refluxing CHCl3,
which was converted into RuCl2(xantphos)(P(OPh)3) and RuCl2(xantphos)(DMSO) by
the reaction with P(OPh)3 and DMSO, respectively. The catalytic activity of these
complexes for the addition of carboxylic acid onto olefins is also described.

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Synthesis of RuCl2(xantphos)L (L = PPh3, P(OPh)3,
DMSO) Complexes, and their Catalytic Activity for the
Addition of Carboxylic Acids onto Olefins
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Shoko Higashi,a Hiroto Takenaka,b Yoshihiko Itob Yohei Oe,a*and Tetsuo Ohtaa
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a) Department of Biomedical Information, Faculty of Life and Medical Sciences, Doshisha University,
Kyotanabe, Kyoto, 610-0321, Japan
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b) Department of Molecular Science and Technology, Faculty of Engineering, Doshisha University,
Kyotanabe, Kyoto, 610-0321, Japan
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E-mail: yoe@mail.doshisha.ac.jp
FAX: +81 774 65 6505
Abstract
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Readily synthesis of a series of RuCl2(xantphos)L (L= PPh3, P(OPh)3, DMSO) was achieved. Thus,
RuCl2(xantphos)PPh3 was synthesised by the reaction of RuCl2(PPh3)3 with xantphos. PPh3 in this
complex is easily exchanged with P(OPh)3 and Dimethylsulfoxide (DMSO) to give
RuCl2(xantphos){P(OPh)3} and RuCl2(xantphos)(DMSO), respectively.
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Introduction
The ligands in transition metal complexes influence the reactivity of these complexes in
Xantphos,1
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homogeneous
and
heterogeneous
catalysis.
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4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene, has received much attention
recently because it produces various effects in transition metal-catalysed reactions, and
therefore,2 many metal complexes such as palladium, rhodium, and iridium complexes
have been synthesised and utilised.3-5 Synthesis and characterisation of xantphos
ruthenium complexes and their application to catalytic organic transformations have
also been reported.6-13 In 2001, Mol synthesised carbene ruthenium complexes
containing the xantphos ligand and investigated its catalytic activity on alkene
metathesis reactions.6 Williams and Whittlesey reported that xantphos-ruthenium
catalysis showed high catalytic activity for the hydrogen transfer alkylation of
cyanoketones with alcohols.7 They also synthesised their original ruthenium
complexes containing xantphos and carbene ligands and investigated their catalytic
activity in the alkylation reaction of cyanoacetoacetates using alcohols as alkylating
reagents.8 Dutta synthesised a RuCl2(CO2)(xantphos) complex and utilised it in the
transfer hydrogenation of carbonyl compounds.9 Whittlesey synthesised the
ruthenium-xantphos complex containing a fluoride ligand.10 In these cases, xantphos
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acts as a bidentate ligand, and the PxantphosRuPxantphos coordination mode is defined to
be cis. Synthesis of RuCl2(xantphos)(DMSO), in which xantphos acts as a POP
tridentate ligand, has been reported by Kharat but with two phosphorus atoms located
at the cis-position.11 The pincer-type ruthenium-xantphos complex is rare. Whittlesey et
al. reported preparation of Ru(xantphos)(PPh3)HCl, in which two phosphorus atoms of
xantphos were located at the trans-position and an oxygen atom was coordinated to the
ruthenium centre like a pincer-type ligand.12 During our ongoing study on ruthenium
catalysis,13 we have found that RuCl2(xantphos)PPh3 can readily be synthesised by the
reaction of RuCl2(PPh3)3 and xantphos and that xantphos behaves as a POP
pincer-type tridentate ligand.14 Here we report the synthesis of RuCl2(xantphos)PPh3,
the reaction of the complex with triphenylphosphite and DMSO, and the catalytic
activity of these complexes for the addition of 2-phenylbenzoic acid onto olefins.
We hypothesised that reaction of RuCl2(PPh3)3 (1) with xantphos would afford a
RuCl2(xantphos)(PPh3) complex. As expected, the reaction of 1 with xantphos was
performed in refluxing CHCl3 for 4.5 h to afford the desired RuCl2(xantphos)(PPh3) (2a)
in 95% yield as a red crystal (Scheme 1).
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31P{1H} NMR, FAB-MS spectra and an ORTEP structure of 2a revealed that xantphos
behaved as a pincer-type ligand. Two phosphorus signals are seen on the 31P{1H} NMR

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spectrum of 2a. One signal appears at 36 ppm as a doublet, and the other at 58 ppm as a
triplet (JPP = 30.6 Hz). The mass number of complex 2a was measured by FAB-MS
spectroscopy to obtain a fragment ion peak at 1012 [m/z]. Recrystallisation of 2a from
CHCl3/Et2O successfully afforded a single crystal. The ORTEP diagram of 2a is shown
in Fig. 1. The xantphos in 2a behaves as a P-O-P pincer-type ligand, and two
phosphorus atoms of xantphos are located at the trans-positions. The oxygen,
ruthenium, and phosphorus atoms in PPh3 are nearly aligned (O-Ru-PPPh3 = 174.48(8)º).
On the other hand, Pxantphos-Ru-Pxantphos is apparently not linear [156.33(3)º],
presumably due to the constraint of forming fused five-membered rings including
oxygen, two phosphorus atoms of xantphos, and ruthenium. During our studies, Vogt et
al. reported that the same complex can be prepared from another ruthenium precursor,
RuCl2(PPh3)4, and xantphos.14
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Next, the ligand exchange reactions of PPh3 of complex 2a with triphenylphosphite and
DMSO were next examined (Scheme 2). Initially, the reaction of 2a with
triphenylphosphite was examined. Treatment of complex 2a with five equivalents of
P(OPh)3 in refluxed CHCl3 afforded RuCl2(xantphos){P(OPh)3} (2b) in 85% yield as a
yellow crystals. The structure of 2b was determined from the 31P{1H} NMR spectrum
and X-ray analysis just as with 2a, indicating that PPh3 was replaced by P(OPh)3

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without loss of the geometry. An ORTEP diagram of 2b is shown in Fig. 2. Therefore, the
less steric repulsion in this complex than in the similar complex 2a leads to a shorter
Ru-P bond length (Ru-PP(OPh)3 = 2.1625(13) Å, Ru-PPPh3 = 2.3338(11) Å), and the
xanthene ring of 2b is almost flat while that of 2a was slightly bent. These are
presumably due to both the smaller cone angles of P(OPh)3 (125°) than PPh3 (145°) and
larger -acceptor ability of P(OPh)3 compared to PPh3.15 The splitting pattern of 2b on
the 31P{1H} NMR spectrum was similar to that of 2a. Thus, a doublet appeared at 40.1
ppm, and a triplet appeared at 124.4 ppm (JPP = 43.4 Hz). Treatment of 2a with DMSO
afforded RuCl2(xantphos)(DMSO) (2c) in 46% yield as a yellow precipitate. We
considered that trans-RuCl2(xantphos)(DMSO) 2c was obtained after the reaction and
that cis-RuCl2(xantphos)(DMSO) (2c’) was formed during recrystallisation of the
obtained complex with CHCl3/DMSO/Et2O. The chemical shifts on 31P{1H} NMR spectra
of 2c and 2c’ are apparently different: a singlet of 2c was observed at 35.4 ppm, and that
of 2c’ was obtained at 47.9 ppm. Interestingly, the reaction of cis-RuCl2(DMSO)4 with
xantphos in refluxed toluene afforded a mixture of 2c and 2c’. The quantity of 2c relative
to 2c’ from RuCl2(xantphos)(PPh3) with DMSO in CDCl3 was apparently higher than
that from cis-RuCl2(DMSO)4. This phenomenon was not observed in Kharat’s report of
2c’, which described the reaction of RuCl2(DMSO)4 and xantphos in CH2Cl2.11 An
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ORTEP diagram of 2c’ is shown in Fig. 3. In complex 2c’, xantphos behaves as a
cis-chelate coordinated ligand. DMSO is coordinate to the ruthenium atom on a sulfur
atom, and the S-Ru-O(xantphos) bond is close to line (S-Ru-Oxantphos = 177.6º). The
xanthene ring is apparently bent due to the cis-coordination of xantphos ligand to the
ruthenium centre. The coordination strength of ligand L (PPh3, P(OPh)3, DMSO) in
RuCl2(xantphos)L was checked in the NMR experiments as follows, and the results are
summarized in Table 1. The complex 2a was reacted with an excess amount of DMSO to
give a mixture of 2a, 2c, and 2c’ (2a : 2c : 2c’ = 23 : 71 : 6). On the other hand, when 2c’
was treated with one equivalent of PPh3 in refluxed CDCl3 for 3 h, the complex 2a was
obtained as a main product (2a : 2c’ = 94 : 6). These results suggested that PPh3 ligand
was more strongly coordinated to Ru centre than DMSO. Comparing the coordination
ability between PPh3 and P(OPh)3 revealed that P(OPh)3 was more coordinated onto the
ruthenium centre than PPh3 ligand. Thus, the reaction of 2b with one equivalent or
even with an excess amount of PPh3 caused no reaction. Therefore, the magnitude of
bond strength of Ru-L in the present system is P(OPh)3>PPh3>DMSO in the same order
as -acidity of these ligands.15
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With xantphos-RuCl2 complexes 2a, 2b, and 2c’ in hand, the catalytic activity of these
complexes in the addition reaction of 2-phenylbenzoic acid (3) onto 4-allylanisole (4a)

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was investigated, and selected results are summarised in Table 2. In the presence of 5
mol % Ru of complex 2a, the reaction was carried out in toluene at 100ºC for 42 h to give
the desired ester 5a in 89% yield (entry 1). The use of complex 2b enabled us to perform
the reaction under milder conditions (at 80ºC), and the product yield was increased to
99% (entry 2). The use of DMSO complex 2c’ afforded 5a in 76% yield (entry 3).
Combined with the ligand exchange reactions described above, it seems that the less
dissociated ligand L should be important for the high catalytic efficiency. With catalyst
2b/2AgOTf (5 mol % Ru), some unactivated olefins were subjected to the addition of
carboxylic acid 3. As in entries 4-7, allylbenzene (4b), 4-phenyl-1-butene (4c), 1-octene
(4d), and cyclohexene (4e) were good substrates to obtain the corresponding esters in
66%, 90%, 80%, and 86% yields, respectively. Catalytic activity of 2b/2AgOTf was as
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high
as
that
of
our
previously
reported
ruthenium
catalysis,
[(p-cymene)RuCl2]2/4AgOTf/xantphos.13 The catalytic activity of TfOH and AgOTf was
tested since a similar reaction is catalysed by TfOH16 or AgOTf17 (Scheme 3). The
reaction of 3 with 4a in the presence of TfOH performed under the same reaction
conditions as those in Table 2 afforded no desired ester 5a, while 62% yield of ester 5a
was obtained at room temperature.18 On the other hand, no reaction took place when 10
mol % of AgOTf was used as a catalyst. These results suggested that the ruthenium

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triflate complexes generated by the treatment of 2b with AgOTf should show the good
catalytic efficiency, probably due to a suitable quantity of TfOH for the activation of
alkenes being formed by the reaction of 2b with 2-phenylbenzoic acid.19
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Conclusions
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A facile synthetic procedure involving the RuCl2(xantphos)L (L = PPh3, DMSO, P(OPh)3)
family has been developed. RuCl2(xantphos)(PPh3) can be synthesised from
commercially available RuCl2(PPh3)3 and xantphos by mixing in refluxing CHCl3 in
high yield. Furthermore, PPh3 can be readily exchanged with P(OPh)3 and DMSO
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without
loss
of
the
core
RuCl2(xantphos)
structure,
though
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trans-RuCl2(xantphos)DMSO was considered to be isomerised to the cis-coordination
complex during the recrystallisation. The strong coordination of P(OPh)3 to the
ruthenium centre led to flat geometry of the xanthene ring and high catalytic activity
for the reaction of carboxylic acid with olefins. The catalytic activities of this family for
the other reactions are being investigated in our laboratory.
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Acknowledgement
We would like to dedicate this article to the memory of our mentor, the late Professor

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Yoshihiko Ito. This work was partially supported by Doshisha University’s Research
Promotion Fund, and a Grant to RCAST at Doshisha University from the Ministry of
Education, Culture, Sports, Science and Technology, Japan. This work was supported
by a Grant-in-Aid for Young Scientists (Start-up: No. 20850034) from JSPS.
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Experimental Section
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General: All solvents are dried and distilled by means of the usual method.20 Xantphos was
perchased from Sigma Aldrich and used without further purifications. P(OPh)3 was perchased from
TCI and used without further purifications. RuCl2(PPh3)3 was prepared according to the literature
procedure.21 1H and 31P{1H} NMR spectra were recorded on Varian Mercury300-N plus (300.0 MHz
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for H and 121.4 MHz for 31P{1H}). FAB MS spectra were recorded on JEOL Mstation JMS-700
spectrometer. X-ray crystallography was performed by use of RIGAKU SCXmini and R-AXIS
RAPID system. All calculations were performed using the Yadokari-XG, software for crystal
structure analyses.22,23
Synthesis of RuCl2(xantphos)PPh3 (2a)14
A dried three-necked round bottom flask equipped with a condenser had RuCl2(PPh3)3 (1) (1.156 g,
1.2 mmol), xantphos (0.7630 g, 1.32 mmol) and dry CHCl3 (50 mL) added under argon atmosphere.
The reaction mixture was refluxed for 3 h with stirring. After the reaction mixture was cooled to

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room temperature, the solvent was removed to ca. 5 mL under reduced pressure, and Et2O (15 mL)
was then added slowly. The resulting mixture was kept until a large enough amount of crystalline
solid was formed. The resulting crystalline solid was filtered, washed three times with 5 mL of
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benzene, and dried in vacuo to give RuCl2(xantphos)PPh3 2a (95%). M.p. = 215-217°C (dec). H
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NMR (CDCl3, 300 MHz)  (ppm) = 1.71 (6H, m, C(CH3)2), 6.75-6.81 (6H, m, ArH), 7.04-7.30
(33H, ArH), 7.47-7.50 (2H, m, ArH). 31P{1H} NMR (CDCl3, 121.4 MHz)  (ppm) = 34.2 (2P, d, Jpp
= 30.6 Hz, xantphos-P), 55.9 (1P, t, Jpp = 30.6 Hz, PPh3-P). FAB-MS (M++PPh3) 1012 (m/z). HRMS
(M+PPh3) calcd ： 1012.1260 ， found ： 1012.1273. Crystallographic data of 2a:
(C57H47Cl2OP3Ru), M = 1012.82, monoclinic, a = 10.3028(14) Å, b = 24.773(3) Å, c = 18.654(3) Å, β =
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102.880(3)o, V = 4641.4(12) Å, space group P21/n (No. 14), Z = 4, 46546 reflections collected, 10572
unique (Rint = 0.0449), R1 (I>2σ(I)) = 0.0756, wR2 (I>2σ(I)) = 0.1401 (all data).
Synthesis of RuCl2(xantphos){P{(OPh)3} (2b)
To an 80 mL schlenk tube was added RuCl2(xantphos)PPh3 2a (101.2 mg, 0.1 mmol),
triphenylphosphite (155.2 mg, 0.5 mmol) and dry CHCl3 (5 mL) in argon atmosphere. The reaction
mixture was heated at 80 ºC (bath temp.) and stirred for 3 h. After the reaction mixture was cooled to
room temperature, the solvent was removed to ca. 1 mL under reduced pressure, and dry Et2O (15
mL) was then added with stirring to form yellow precipitation. The obtained solid was filtered and
washed with three times of 1 mL of Et2O. The residual solid was dried in vacuo to give

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RuCl2(xantphos){P(OPh)3} 2b. M.p. = 281.4-282.1°C (dec). 1H NMR (CDCl3, 300 MHz)  (ppm) =
1.79 (6H, m, C(CH3)2), 6.43-6.46 (6H, m, ArH), 6.84-6.93 (9H, m, ArH), 7.11-7.32 (16H, ArH),
7.61-7.63 (2H, m, ArH), 7.71-7.77 (8H, m, ArH). 31P{1H} NMR (CDCl3, 121.4 MHz)  (ppm) =
40.1 (2P, d, Jpp = 43.4 Hz, 2P of xantphos), 124.4 (1P, t, Jpp = 43.4 Hz, P(OPh)3). HRMS (FAB, M+)
calcd：1060.1108，found：1060.1123. Crystallographic data of 2b: (C57H47Cl2O4P3Ru · CHCl3), M
= 1180.19, triclinic, a = 11.5019(3) Å, b = 13.0630(3) Å, c = 18.7270(5) Å, α = 84.429(2)o, β =
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73.328(2)o, γ = 79.099(2)o, V = 2644.06(12) Å, space group P-1 (No.2), Z = 2, 26596 reflections
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collected, 9288 unique (Rint = 0.0779), R1 (I>2σ(I)) = 0.0760, wR2 (I>2σ(I)) = 0.2056 (all data).
Synthesis of RuCl2(xantphos)(DMSO) (2c’)12
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To an 80 mL schlenk tube was added RuCl2(xantphos)PPh3 2a (101.2 mg, 0.1 mmol), dimethyl
sulfoxide (1 mL) and dry CHCl3 (4 mL) in argon atmosphere. The reaction mixture was heated at 80
ºC (bath temp.) and stirred for 3 h. After the reaction mixture was cooled to room temperature, the
solvent was removed to ca. 1 mL under reduced pressure, and dry Et2O (15 mL) was then added with
stirring to form yellow precipitation. The obtained solid was filtered, and the residue was washed
with tree times of 1 mL of Et2O. The residual solid was dried in vacuo to give a mixture of cis- and
trans-RuCl2(xantphos)(DMSO) (2c’ and 2c), and the recrystallization of this product afforded 2c’.
M.p. = 242.3-242.8°C (dec).

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2c’: 1H NMR (CDCl3, 300 MHz)  (ppm) = 1.70 (6H, s, C(CH3)2), 2.77 (6H, s, S(CH3)2), 6.59-6.64
(4H, m, ArH), 6.84-6.89 (2H, m, ArH), 6.98-7.04 (4H, m, ArH), 7.28-7.40 (10H, m, ArH), 7.42-7.57
(2H, m, ArH), 7.98-8.04 (4H, m, ArH). 31P{1H} NMR (CDCl3, 121.4 MHz)  (ppm) = 47.9 (s, P of
xantphos). FAB-MS (MCl) 793 (m/z). 2c: 1P{1H} NMR (CDCl3, 121.4 MHz)  (ppm) = 35.4 (s, P
of xantphos). Crystallographic data of 2c’: (C42H38Cl2O2P2RuS1 • CH6OS), monoclinic, M =
906.81, a = 13.8705(3) Å, b = 14.5270(4) Å, c = 21.6728(7) Å, β = 107.968(2)o, V =
4154.0(2) Å3, space group P21/c (No. 14), Z = 4, 40636 reflections collected, 7566 unique (Rint =
0.1723), R1 (I>2σ(I)) = 0.1323, wR2 (I>2σ(I)) = 0.2777 (all data).
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Notes and references
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a Department of Biomedical Information, Faculty of Life and Medical Sciences,
Doshisha University, Kyotanabe, Kyoto Japan 610-0394. Fax: +81 774 65 6505; Tel: +81
774 6505; E-mail:yoe@mail.doshisha.ac.jp
b Department of Molecular Science and Technology, Faculty of Engineering, Doshisha
University
† Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/b000000x/

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1
For reviews, see, (a) P. W. N. M. van Leeuwen, P. C. J. Kamer, J. N. H. Reek, P. Dierkes, Chem.
Rev. 2000, 100, 2741. (b) P. C. J. Kamer, P. W. N. M. van Leeuwen, J. N. H. Reek, Acc. Chem.
Res. 2001, 34, 895. (c) Z. Freixa, van P. W. N. M. Leeuwen, Dalton Trans. 2003, 1890-1901.
For recent examples, see: [Pd] (a) H. Kelgtermans, L. Dobrzanska, L. V. Meervelt, W. Dehaen,
Org. Lett. 2012, 14, 1500. (b) D. N. Sawant, Y. S. Wagh, K. D. Bhatte, B. M. Bhanage, Eur. J.
Org. Chem. 2011, 6719. (c) M. A. Soussi, D. Audisio, S. Messaoudi, O. Provot, J.-D. Brion, M.
Alami, Eur. J. Org. Chem. 2011, 5077. (d) G.-B. Deng, Z.-Q. Wang, R.-J. Song, M.-B. Zhou,
W.-T. Wei, P. Xie, J.-H. Li, Chem. Commun. 2011, 47, 8151. (e) D. N. Sawant, Y. S. Wagh, K. D.
Bhatte, B. M. Bhanage, J. Org. Chem. 2011, 76, 5489. (f) D. Fujino, H. Yorimitsu, K. Oshima, J.
Am. Chem. Soc. 2011, 133, 9682. (g) Y. Zhao, J. Hu, Angew. Chem. Int. Ed. 2012, 51, 1033. (h) J.
Mo, D. Eom, S. Kim, H. Sung, P.H. Lee, Chem. Lett. 2011, 40, 980. (i) Y. Zhao, J. Hu, Angew.
Chem. Int. Ed. 2012, 51, 1033. (j) B. Li, L. Samp, J. Sagal, C. M. Hayward, C. Yang, Z. Zhang, J.
Org. Chem. 2013, 78, 1273. (k) S.-C. Sha, J. Zhang, P. J. Carroll, P. J. Walsh, J. Am. Chem. Soc.
2013, 135, 17602. (l) M. M. Lorion, D. Gasperini, J. Oble, G. Poli, Org. Lett. 2013, 15, 3050. (m)
S. P. Schröder, N. J. Taylor, P. Jackson, V. Franckevicius, Org. Lett. 2013, 15, 3778. (n) F. M.
Miloserdov, C. L. McMullin, M. M. Belmonte, J. B.-Buchholz, V. I. Bakhmutov, S. A.
Macgregor, V. V. Grushin, Organometallics, 2014, 33, 736. (o) K. K. A. Khader, A. M. Sajith, M.
S. A. Padusha, H. P. Nagaswarupa, A. Muralidharan, Tetrahedron Lett. 2014, 55, 1778. (p) D.
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Fujino, H. Yorimitsu, A. Osuka, J. Am. Chem. Soc. 2014, 136, 6255. (q) M.-N. Zhao, Z.-H. Ren,
Y.-Y. Wang, Z.-H. Guan, Org. Lett. 2014, 16, 608. (r) Z. Feng, Q.-Q. Min, Y.-L. Xiao, B. Zhang,
X. Zhang, Angew. Chem. Int. Ed. 2014, 53, 1669. (s) J. Hwang, K. Park, J. Choe, H. Min, K. H.
Song, S. Lee, J. Org. Chem. 2014, 79, 3267. (t) X. Fang, H. Li, R. Jackstell, M. Beller, Angew.
Chem. Int. Ed. 2014, 53, 9030. (u) D. Falcone, E. Osimboni, D. J. Guerin. Tetrahedron Lett.
2014, 55, 2646. (v) J. Carrillo, A. Gómez, A. M. Costa, P. Fernández, C. Isart, M. Sidera, J.
Vilarrasa, Tetrahedron Lett. 2014, 55, 4623. (w) B. Wong, X. Linghu, J. J. Crawford, J. Drobnick,
W. Lee, H. Zhang, Tetrahedron, 2014, 70, 1508. [Rh] (a) O. Diebolt, C. Cruzeuil, C. Mueller, D.
Vogt, Adv. Synth. Catal. 2012, 354, 670. (b) M. Tobisu, H. Kinuta, Y. Kita, E. Remond, N.
Chatani, J. Am. Chem. Soc. 2012, 134, 115. (c) A. B. Khemnar, D. N. Sawant, B. M. Bhanage,
Tetrahedron Lett. 2013, 54, 2682. [Ru] (a) A. J. A. Watson, A. C. Maxwell, J. M. J. Williams,
Org. Biomol. Chem. 2012, 10, 240. (b) S. Imm, S. Bähn, M. Zhang, L. Neubert, H. Neumann, F.
Klasovsky, J. Pfeffer, T. Haas, M. Beller, Angew. Chem. Int. Ed. 2011, 50, 7599. (c) H. Miura, K.
Wada, S. Hosokawa, M. Inoue, Chem. Eur. J. 2013, 19, 861. (d) M. Zhang, X. Fang, H.
Neumann, M. Beller, J. Am. Chem. Soc. 2013, 135, 11384. (e) F.-X. Yan, M. Zhang, X.-T. Wang,
F. Xie, M.-M. Chen, H. Jiang, Tetrahedron, 2014, 70, 1193. [Cu] (a) H. Ito, T. Miya, M.
Sawamura, Tetrahedron, 2012, 68, 3423. (b) H.-Y. Jung, X. Feng, H. Kim, J. Yun, Tetrahedron,
2012, 68, 3444. (c) H. Ito, K. Kubota, Org. Lett. 2012, 14, 890. (d) H. Zheng, J. Ding, J. Chen,
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18

ACCEPTED MANUSCRIPT
1
2
M. Liu, W. Gao, H. Wu, Synlett, 2011, 11, 1626. (e) R. Alfaro, A. Parra, J. Alemꢀn, J. L. G.
Ruano, M. Tortosa, J. Am. Chem. Soc. 2012, 134, 15165. (f) K. Kubota, E. Yamamoto, H. Ito, J.
Am. Chem. Soc. 2013, 135, 2635. (g) G. He, S. Chen, Q. Wang, H. Huang, Q. Zhang, D. Zhang,
R. Zhang and H. Zhu, Org. Biomol. Chem. 2014, 12, 5945. (h) Y. Zhou, W. You, K. B. Smith, M.
K. Brown, Angew. Chem. Int. Ed. 2014, 53, 3475. [Co] (a) Z. Ding, N. Yoshikai, Synthesis, 2011,
16, 2561. (b) B. Wu, N. Yoshikai, Angew. Chem. Int. Ed. 2013, 52, 10496. (c) K. Gao, N.
Yoshikai, Acc. Chem. Res. 2014, 47, 1208. [Ni] (a) P. Kumar, S. Prescher, J. Louie, Angew.
Chem. Int. Ed. 2011, 50, 10694. [Fe] (a) T. Hatakeyama, T. Hashimoto, K. K. A. D. S.
Kathriarachchi, T. Zenmyo, H. Seike, M. Nakamura, Angew. Chem. Int. Ed. 2012, 51, 8834. (b)
M. Sekine, L. Ilies, E. Nakamura, Org. Lett. 2013, 15, 714.
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
3
For examples of Rh complexes, see: (a) G. L. Williams, C. M. Parks, R. C. Smith, H. Adams,
A. Haynes, A. J. H. M. Meijer, G. J. Sunley, S. Gaemers, Organometallics, 2011, 30, 6166. (b) M.
Kranenburg, Y. E. M. van der Burgt, P. C. J. Kamer, P. W. N. M. van Leeuwen, K. Goubitz, J.
Fraanje, Organometallics, 1995, 14, 3081. (c) R. J. van Haaren, E. Zuidema, J. Fraanje, K.
Goubitz, P. C. J. Kamer, P. W. N. M. van Leeuwen, G. P. F. van Strijdonck, C. R. Chimie, 2002, 5,
431. (d) R. J. Pawley, G. L. Moxham, R. Dallanegra, A. B. Chaplin, S. K. Brayshaw, A. S. Weller,
M. C. Willis, Organometallics, 2010, 29, 1717. (e) H. C. Johnson, E. M. Leitao, G. R. Whittell, I.
Manners, G. C. L.-Jones, A. S. Weller, J. Am. Chem. Soc. 2014, 136, 9078.

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1
2
4
For examples of Pd complexes, see: (a) J. R. Martinelli, D. A. Watson, D. M. M. Freckmann,
T. E. Barder, S. L. Buchwald, J. Org. Chem. 2008, 73, 7102. (b) A. M. Johns, M. Utsunomiya, C.
D. Incarvito, J. F. Hartwig, J. Am. Chem. Soc. 2006, 128, 1828. (c) K. Fujita, M. Yamashita, F.
Puschmann, M. M. Alvarez-Falcon, C. D. Incarvito, J. F. Hartwig, J. Am. Chem. Soc. 2006, 128,
9044. (d) V. V. Grushin and W. J. Marshall, J. Am. Chem. Soc. 2006, 128, 12644. (e) K. Saikia, B.
Deb, B. J. Borah, P. P. Sarmah, D. K. Dutta, J. Organomet. Chem. 2012, 696, 4293. (f) M. A.
Zuideveld, B. H. G. Swennenhuis, M. D. K. Boele, Y. Guari, G. P. F. van Strijdonck, J. N. H.
Reek, P. C. J. Kamer, K. Goubitz, J. Fraanje, M. Lutz, A.L. Spek, P. W. N. M. van Leeuwen, J.
Chem. Soc., Dalton Trans. 2002, 2308.
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
5
Ir complexes: (a) A. J. Pontiggia, A. B. Chaplin, A. S. Weller, J. Organomet. Chem. 2011,
696, 2870. (b) D. J. Fox, S. B. Duckett, C. Flaschenriem, W. W. Brennessel, J. Schneider, A.
Gunay, R. Eisenberg, Inorg. Chem. 2006, 45, 7197.
6
7
8
P. Nieczypor, P. W. N. M. van Leeuwen, J. C. Mol, M. Lutz, A. L. Spek, J. Organomet. Chem.
2001, 625, 58.
A. E. W. Ledger, P. A. Slatford, J. P. Lowe, M. F. Mahon, M. K. Whittlesey, J. M. J. Williams,
Dalton Trans. 2009, 4, 716.
A. E.W. Ledger, M. F. Mahon, M. K. Whittlesey, J. M. J. Williams, Dalton Trans. 2009, 35,
6941.

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1
2
9
B. Deb, B. J. Borah, B. J. Sarmah, B. Das, D. K. Dutta, Inorg. Chem. Commun. 2009, 12, 868.
10 L. M. Guard, A. E. W. Ledger, S. P. Reade, C. E. Ellul, M. F. Mahon, M. K. Whittlesey, J.
Organomet. Chem. 2011, 696, 780.
3
4
11 A. N. Kharat, A. Bakhoda, B. T. Jahromi, Inorg. Chem. Commun. 2011, 14, 1161.
12 A. E. W. Ledger, A. Moreno, C. M. Ellul, M. F. Mahon, P. S. Pregosin, M.K. Whittlesey,
J.M.J. Williams, Inorg. Chem. 2010, 49, 7244.
5
6
7
13 Y. Oe, T. Ohta, Y. Ito, Tetrahedron Lett. 2010, 51, 2806.
8
14
(a) D. Pingen, M. Lutz, D. Vogt, Organometallics, 2014, 33, 1623. (b) D. Pingen, Tomas Lebl,
Martin Lutz, Gary S. Nichol, Paul C. J. Kamer, D. Vogt, Organometallics, 2014, 33, 2798.
C.A. TOLMAN, Chem. Rev. 1977, 77, 313, and the references there in.
D. C. Rosenfeld, S. Shekhar, A. Takemiya, M. Utsunomiya, J. F. Hartwig, Org. Lett. 2006, 8,
4179.
9
10
11
12
13
14
15
16
17
18
15
16
17
C.-G. Yang, N. W. Reich, Z. Shi, C. He, Org. Lett. 2005, 7, 4553.
18 Z. Li, J. Zhang, C. Brouwer, C.-G. Yang, N. W. Reich, C. He, Org. Lett. 2006, 8, 4175.
19 T. T. Dang, F. Boeck, L. Hintermann, J. Org. Chem., 2011, 76, 9353.
20 D. D. Perrin, W. L. F. Armarego, “Purification of Laboratory Chemicals”, 3rd Ed. Pergamon
Press (1988).
21 P. S. Hallman, T. A. Stephanson, G. Wilkinson, Inorg. Chem. 1970, 12, 237.

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5
22 K. Wakita (2001); Release of Software (Yadokari-XG 2009) for Crystal Structure Analyses, see
C. Kabuto, S. Akine, T. Nemoto, and E. Kwon, J. Cryst. Soc. Jpn., 2009, 51, 218.
23 CCDC 1035410 (for 2a), 1035411 (for 2b) and 1035412 (for 2c) contains the supplementary
crystallographic data for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
6

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PPh2
PPh2
Cl
+
O
RuCl2(PPh3)3
O
Ru PPh3
CHCl3, reflux
4.5 h
Cl
1
PPh2
PPh2
2a (95% yield)
1
2
Scheme 1 Preparation of RuCl2(xantphos)(PPh3) (2a).
3
PPh2
Cl
PPh2
Cl
O
Ru PPh3
L
O
Ru
L
+
Cl
Cl
PPh2
PPh2
2a
2b: L = P(OPh)3
2c: L = DMSO
4
5
Scheme 2 Reaction of 2a with P(OPh)3 and DMSO.
6
TfOH
(2 mol %)
3
+
+
4a
4a
5a
toluene
0% yield (80oC, 24 h)
62% yield (rt, 42 h)
AgOTf
(10 mol %)
3
5a
toluene
80oC, 42 h
0% yield
(>99% recovery of 4a)
7
8
Scheme 3 Catalytic activity of TfOH and AgOTf.
9

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P3
Cl1
P1
Ru1
O1
P2
Cl2
1
2
Fig.1 ORTEP diagram of 2a. All hydrogen atoms are omitted for clarity. Ellipsoids are shown at the 50% probability
level. Selected bond length (Å) and angles: Ru-P1 2.4088(10), Ru-P2 2.3355(10), Ru-P3 2.3338(9), Ru-O1 2.315(2),
P3-Ru-O1 174.48(8), P1-Ru-P2 156.33(3).
3
4
O4
O3
Cl1
P2
O1
P3
O2
Ru1
Cl2
P1
5
6
7
8
Fig.2 ORTEP diagram of 2b. All hydrogen atoms are omitted for clarity. Ellipsoids are shown at the 50% probability
level. Selected bond length (Å) and angles: Ru-P1 2.3381(10), Ru-P2 2.3225(11), Ru-P3 2.1625(14),
Ru-O1(2.265(3),P3-Ru-O1 175.83(7), P1-Ru-P2 161.23(5), Cl1-Ru-Cl2 167.86(4).

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S1
Cl1
O2
Ru1
P1
Cl2
P2
O1
1
2
3
4
Fig.3 ORTEP diagram of 2c’. All hydrogen atoms are omitted for clarity. Ellipsoids are shown at the 50% probability
level. Selected bond length (Å) and angles: Ru1-S1 2.213(2), Ru1-P1 2.271(2), Ru-P2 2.339(2), Ru1-O1 2.183(5),
Cl1-Ru-Cl2 85.40(8), P1-Ru-P2 103.78(8), S1-Ru1-O1 177.58(19).
5
6
Table 1 Ligand exchange reactions of RuCl2(xantphos)L with external ligands.a
7
8
entry
complex
2a
ligand
Yieldb
1
2
3
4
DMSO (0.2 mL)
PPh3 (1 eq)
2a (23%) : 2c (71%) : 2c’ (6%)
2a (94%) : 2c (6%) : 2c’ (0%)
2b (100%) : 2a (0%)
2c’
PPh3 (1 eq)
2b
PPh3 (50 eq)
2b (100%) : 2a (0%)
2b
9
10
11
a Reaction conditions: Ru complex (0.02 mmol) and Ligand were stirred in refluxed CDCl3 for 3
b
h, and then the reaction mixture was cooled to ambient temperature. Determined by 31P
NMR.
12

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1
2
Table 2 Reaction Products of 2-Phenylbenzoic Acid with Olefins in the Presence of Ruthenium Catalysisa
O
O
Ru Complex (5 mol %)
AgOTf (10 mol %)
OH
O
R
R
4a-e
+
toluene, 80 ºC, 42 h
Ph
Ph
3
5a-e
Entry
Ru Complex
Olefin
Product
Yield (%)b
1c
2
2a
2b
2c
89
99
76
3c
4
5
6
7
2b
2b
2b
2b
66
90
80
86
3
4
5
6
a Reaction conditions: Ru complex (0.05 mmol) and AgOTf (0.10 mmol) were stirred in refluxed toluene for 3 h, and
then the reaction mixture was cooled to ambient temperature. To the reaction mixture, nucleophile (1.0 mmol) and
olefin (3.0 mmol) was added and degassed by freeze-pump-thaw cycle (3 cycles). The solution was stirred at 80 ºC
for 42 h. b Yields were determined by 1H NMR by using anthracene as an internal standard. c at 100oC.

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Highlights
ꢀ
ꢀ
ꢀ
RuCl2(xantphos)(PPh3) was readily synthesized by the mixing of RuCl2(PPh3)3 with
xantphos in refluxing CHCl3.
RuCl2(xantphos)(PPh3) was readily converted into RuCl2(xantphos)(P(OPh)3) and
RuCl2(xantphos)(DMSO) through the ligand exchange reaction.
RuCl2(xantphos)(P(OPh)3) showed the highest catalytic activity in the addition
reaction of carboxylic acids with olefins among these three complexes.

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Supplementary Data for
Synthesis of RuCl2(Xantphos)L (L = PPh3, P(OPh)3, DMSO)
Complexes, and their Catalytic Activity for the Addition of 2-
Phenylbenzoic Acid onto Olefins
Shoko Higashi, Hiroto Takenaka, Yoshihiko Ito, Yohei Oe,* and Tetsuo Ohta
yoe@mail.doshisha.ac.jp
Department of Biomedical Information, Faculty of Life and Medical Sciences, Doshisha University,
Kyotanabe, Kyoto 610-0321, Japan
Synthesis of RuCl2(xantphos)PPh3 (2a)
A dried three-necked round bottom flask equipped with a condenser had RuCl2(PPh3)3 (1) (1.156 g,
1.2 mmol), xantphos (0.7630 g, 1.32 mmol) and dry CHCl3 (50 mL) added under argon atmosphere.
The reaction mixture was refluxed for 3 h with stirring. After the reaction mixture was cooled to
room temperature, the solvent was removed to ca. 5 mL under reduced pressure, and Et2O (15 mL)
was then added slowly. The resulting mixture was kept until a large enough amount of crystalline
solid was formed. The resulting crystalline solid was filtered, washed three times with 5 mL of
1
benzene, and dried in vacuo to give RuCl2(xantphos)PPh3 2a (95%). M.p. = 215-217°C (dec). H
NMR (CDCl3, 300 MHz) δ (ppm) = 1.71 (6H, m, C(CH3)2), 6.75-6.81 (6H, m, ArH), 7.04-7.30
(33H, ArH), 7.47-7.50 (2H, m, ArH). 31P{1H} NMR (CDCl3, 121.4 MHz) δ (ppm) = 34.2 (2P, d, Jpp
= 30.6 Hz, xantphos-P), 55.9 (1P, t, Jpp = 30.6 Hz, PPh3-P). FAB-MS (M++PPh3) 1012 (m/z). HRMS
(M+−PPh3) calcd ： 1012.1260 ， found ： 1012.1273. Crystallographic data of 2a:
(C57H47Cl2OP3Ru), M = 1012.82, monoclinic, a = 10.3028(14) Å, b = 24.773(3) Å, c = 18.654(3)

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Å, β = 102.880(3)o, V = 4641.4(12) Å3, space group P21/n (No. 14), Z = 4, 46546 reflections
collected, 10572 unique (Rint = 0.0449), R1 (I>2σ(I)) = 0.0756, wR2 (I>2σ(I)) = 0.1401 (all data).
Synthesis of RuCl2(xantphos){P{(OPh)3} (2b)
To an 80 mL schlenk tube was added RuCl2(xantphos)PPh3 2a (101.2 mg, 0.1 mmol),
triphenylphosphite (155.2 mg, 0.5 mmol) and dry CHCl3 (5 mL) in argon atmosphere. The reaction
mixture was heated at 80 ºC (bath temp.) and stirred for 3 h. After the reaction mixture was cooled to
room temperature, the solvent was removed to ca. 1 mL under reduced pressure, and dry Et2O (15
mL) was then added with stirring to form yellow precipitation. The obtained solid was filtered and
washed with three times of 1 mL of Et2O. The residual solid was dried in vacuo to give
RuCl2(xantphos){P(OPh)3} 2b. M.p. = 281.4-282.1°C (dec). 1H NMR (CDCl3, 300 MHz) δ (ppm) =
1.79 (6H, m, C(CH3)2), 6.43-6.46 (6H, m, ArH), 6.84-6.93 (9H, m, ArH), 7.11-7.32 (16H, ArH),
7.61-7.63 (2H, m, ArH), 7.71-7.77 (8H, m, ArH). 31P{1H} NMR (CDCl3, 121.4 MHz) δ (ppm) =
40.1 (2P, d, Jpp = 43.4 Hz, 2P of xantphos), 124.4 (1P, t, Jpp = 43.4 Hz, P(OPh)3). HRMS (FAB, M+)
calcd：1060.1108，found：1060.1123. Crystallographic data of 2b: (C57H47Cl2O4P3Ru · CHCl3), M =
1180.19, triclinic, a = 11.5019(3) Å, b = 13.0630(3) Å, c = 18.7270(5) Å, α = 84.429(2)o, β =
73.328(2)o, γ = 79.099(2)o, V = 2644.06(12) Å3, space group P-1 (No.2), Z = 2, 26596 reflections
collected, 9288 unique (Rint = 0.0779), R1 (I>2σ(I)) = 0.0760, wR2 (I>2σ(I)) = 0.2056 (all data).
Synthesis of RuCl2(xantphos)(DMSO) (2c’)
To an 80 mL schlenk tube was added RuCl2(xantphos)PPh3 2a (101.2 mg, 0.1 mmol), dimethyl
sulfoxide (1 mL) and dry CHCl3 (4 mL) in argon atmosphere. The reaction mixture was heated at 80
ºC (bath temp.) and stirred for 3 h. After the reaction mixture was cooled to room temperature, the
solvent was removed to ca. 1 mL under reduced pressure, and dry Et2O (15 mL) was then added with
stirring to form yellow precipitation. The obtained solid was filtered, and the residue was washed
with tree times of 1 mL of Et2O. The residual solid was dried in vacuo to give a mixture of cis- and

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trans-RuCl2(xantphos)(DMSO) (2c’ and 2c), and the recrystallization of this product afforded 2c’.
M.p. = 242.3-242.8°C (dec).
2c’: 1H NMR (CDCl3, 300 MHz) δ (ppm) = 1.70 (6H, s, C(CH3)2), 2.77 (6H, s, S(CH3)2), 6.59-6.64
(4H, m, ArH), 6.84-6.89 (2H, m, ArH), 6.98-7.04 (4H, m, ArH), 7.28-7.40 (10H, m, ArH), 7.42-7.57
(2H, m, ArH), 7.98-8.04 (4H, m, ArH). 31P{1H} NMR (CDCl3, 121.4 MHz) δ (ppm) = 47.9 (s, P of
xantphos). FAB-MS (M−Cl) 793 (m/z). 2c: 1P{1H} NMR (CDCl3, 121.4 MHz) δ (ppm) = 35.4 (s, P
of xantphos). Crystallographic data of 2c’: (C42H38Cl2O2P2RuS1 • CH6OS), monoclinic, M =
906.81, a = 13.8705(3) Å, b = 14.5270(4) Å, c = 21.6728(7) Å, β = 107.968(2)o, V =
4154.0(2) Å3, space group P21/c (No. 14), Z = 4, 40636 reflections collected, 7566 unique (Rint =
0.1723), R1 (I>2σ(I)) = 0.1323, wR2 (I>2σ(I)) = 0.2777 (all data).
Typical procedure of addition Reaction of Nucleophiles onto olefins catalyzed by
RuCl2(xantphos){P(OPh3)}/2AgOTf: To
a
dried 80 mL schlenk tube was added
RuCl2(xantphos){P(OPh)3} 2b (0.0531 g, 0.05 mmol), AgOTf (0.0257 g, 0.1 mmol) and 3.0 mL of
toluene under argon atmosphere. The catalyst mixture was degassed by three times of Freeze-Pump-
Thaw cycle, and then the tube was filled with argon again. The reaction mixture was stirred at 110
ºC (bath temp.) for 3 h. After cooling to ambient temperature, 2-phenylbenzoic acid 3 (0.1982 g, 1.0
mmol) and olefin (2.5 mmol) was added to the resulting mixture. The solution was degassed by three
times of Freeze-Pump-Thaw cycle and then filled with argon again. The reaction mixture was stirred
1
at 80 ºC (bath temp.) for 42 h. The product yield was determined by H NMR spectrum in CDCl3
using anthrathene as an internal standard. The product was purified through silica gel column
1
chromatography (Hexane/Ethyl Acetate = 10/1). All products were characterized by H and 13C
NMR and FAB MS spectra according to the previous our report.S1
1-(4-Methoxyphenyl)propan-2-yl 2-phenylbenzoate (5a). Yielded from 3 with 4-allylanisole (4a)
as colorless viscous oil. 1H NMR (CDCl3, 300 MHz) δ 1.33 (3H, d, J = 6.3 Hz, CH3), 2.84 (1H, dd, J
= 6.9 Hz, 13.5 Hz, 1/2CH2), 3.01 (1H, dd, J = 6.3 Hz, 13.8 Hz, 1/2CH2), 3.77 (3H, s, MeO), 5.31
(1H, sextet, J = 6.9 Hz, OCH), 6.77-6.87 (2H, m, aromatics), 7.14-7.17 (2H, m, aromatics), 7.39-

ACCEPTED MANUSCRIPT
7.44 (3H, m, aromatics), 7.51-7.56 (1H, m, aromatics), 7.99-8.02 (1H, m, aromatics). 13C NMR
(CDCl3, 75 MHz) δ 132.5, 130.2, 129.3, 128.5, 113.5, 72.2, 55.1, 41.3, 19.4. FAB-MS (m/z) = 347
[M + H+]. CAS Registry No: 1232133-20-8.
1-Phenylpropan-2-yl 2-phenylbenzoate (5b). Yielded from 3 with allylbenzene (4b) as colorless
oil. 1H NMR (CDCl3, 300 MHz) δ 1.04 (3H, d, J = 6.3 Hz, CH3), 2.53 (1H, dd, J = 6.9 Hz, 13.5 Hz,
1/2CH2), 2.76 (1H, dd, J = 6.3 Hz, 13.8 Hz, 1/2CH2), 5.13 (1H, sextet, J = 6.3 Hz, OCH), 7.08-7.11
(2H, m, aromatics), 7.16-7.29 (5H, m, aromatics), 7.32-7.41 (5H, m, aromatics), 7.47-7.52 (1H, m,
aromatics), 7.69-7.71 (1H, m, aromatics). 13C NMR (CDCl3, 75 MHz) δ 168.0, 142.1, 141.3, 137.3,
131.5, 130.8, 130.4, 129.4, 129.3, 128.4, 128.2, 128.0, 127.1, 126.9, 126.3, 72.4, 41.8, 18.9. FAB-
MS (m/z) = 317 [M + H+]. CAS Registry No: 1232133-21-9.
1-Phenylbutan-3-yl 2-phenylbenzoate (5c). Yielded from 3 with 4-phenyl-1-butene (4c) as
colorless oil. 1H NMR (CDCl3, 300 MHz) δ 1.07 (3H, d, J = 6.3 Hz, CH3), 1.64 (2H, m, CH2), 2.42
(2H, m, CH2), 4.92 (1H, sextet, J = 6.3 Hz, OCH), 7.06-7.43 (8H, m, aromatics), 7.50-7.53 (1H, m,
aromatics), 7.78 (1H, d, J = 6.8 Hz, aromatics). 13C NMR (CDCl3, 75 MHz) δ 168.6, 142.4, 141.8,
132.0, 131.2, 130.9, 129.8, 128.8, 128.6, 128.5, 128.3, 127.5, 127.4, 126.1, 71.8, 37.7, 31.8, 19.8.
FAB-MS (m/z) = 317 [M + H+]. CAS Registry No: 1232133-23-1.
1
2-Octyl 2-phenylbenzoate (5d). Yielded from 3 with 1-octene (4d) as light yellow oil. H NMR
(CDCl3, 300 MHz) δ 0.78 (3H, t, J = 7.5 Hz, CH3), 0.84-0.96 (2H, m, CH2), 1.05 (3H, d, J = 6.3 Hz,
CH3), 1.14-1.48 (9H, m, 4CH2), 4.92 (1H, sextet, J = 6.3 Hz, OCH), 7.33-7.54 (8H, m, aromatics),
7.81-7.85 (1H, m, aromatics). 13C NMR (CDCl3, 75 MHz) δ168.6, 142.4, 141.8, 132.2, 131.1, 130.9,
130.8, 129.7, 128.7, 128.2, 128.2, 127.4, 127.3, 72.3, 35.9, 33.4, 32.1, 32.1, 29.5, 26.8, 25.5, 25.2,
23.0, 23.0, 22.9, 19.8, 14.5, 9.9. FAB-MS (m/z) = 311 [M + H+]. CAS Registry No: 1232133-24-2.
Cyclohexyl 2-phenylbenzoate (5e). Yielded from 3 with cyclohexene (4e) as colorless oil. 1H NMR
(CDCl3, 300 MHz) δ 1.07-1.31 (5H, m, cyclohexyl-H), 1.41 (5H, m, cyclohexyl-H), 4.73-4.80 (1H,
m, OCOCH), 7.29-7.48 (8H, m, aromatics), 7.51-7.81 (1H, m, aromatics). 13C NMR (CDCl3, 75
MHz) δ 168.1, 142.0, 141.4, 131.8, 130.7, 130.5, 129.5, 128.3, 127.9, 127.0, 126.9, 73.4, 31.2, 25.3,
23.6. FAB-MS (m/z) = 280 [M+]. CAS Registry No: 1232133-25-3.