Ruthenium indenylidene complexes containing dichalcogenoimidodiphosphinate ligands

Article abstract of DOI:10.1016/j.molstruc.2012.03.007

Reactions of ruthenium indenylidene starting material [Ru(PPh ₃)₂(Ind)Cl₂] (Ind = 3-phenylinden-1-ylidene) with potassium dichalcogenoimidodiphosphinates K[R₂P(E)NP(E′) R₂] afforded a series of complexes [Ru(PPh₃)(Ind){E, E′-R₂P(E)NP(E′)R₂}Cl] [R = Ph, E = E′ = S (1a); R = Ph, E = E′ = Se (1b); R = ⁱPr, E = E′ = S (1c); R = ⁱPr, E = E′ = Se (1d); R = Ph, E = S, E′ = Se (1e); R = ⁱPr, E = S, E′ = Se (1f)] which were characterized by microanalyses, IR and NMR spectroscopies. The molecular structure of 1a has been confirmed by single-crystal X-ray diffraction. The catalytic reactivity of the ruthenium indenylidene complexes in the ring closing metathesis of diethyl 1,2-diallylmalonate has also been investigated.

Full text of DOI:10.1016/j.molstruc.2012.03.007

Journal of Molecular Structure 1019 (2012) 27–31
Contents lists available at SciVerse ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Ruthenium indenylidene complexes containing
dichalcogenoimidodiphosphinate ligands
a
b
c
a,b,
Ai-Quan Jia a, , Zhi-Feng Xin , Qun Chen , Wa-Hung Leung , Qian-Feng Zhang
⇑
⇑
a Institute of Molecular Engineering and Applied Chemistry, Anhui University of Technology, Ma’anshan, Anhui 243002, PR China
b Department of Applied Chemistry, School of Petrochemical Engineering, Changzhou University, Jiangsu 213164, PR China
c Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Reactions of ruthenium indenylidene starting material [Ru(PPh3)2(Ind)Cl2] (Ind = 3-phenylinden-
1-ylidene) with potassium dichalcogenoimidodiphosphinates K[R2P(E)NP(E0)R2] afforded a series of com-
plexes [Ru(PPh3)(Ind){rE,rE0-R2P(E)NP(E0)R2}Cl] [R = Ph, E = E0 = S (1a); R = Ph, E = E0 = Se (1b); R = iPr,
E = E0 = S (1c); R = iPr, E = E0 = Se (1d); R = Ph, E = S, E0 = Se (1e); R = iPr, E = S, E0 = Se (1f)] which were char-
acterized by microanalyses, IR and NMR spectroscopies. The molecular structure of 1a has been con-
firmed by single-crystal X-ray diffraction. The catalytic reactivity of the ruthenium indenylidene
complexes in the ring closing metathesis of diethyl 1,2-diallylmalonate has also been investigated.
Ó 2012 Elsevier B.V. All rights reserved.
Received 11 January 2012
Received in revised form 3 March 2012
Accepted 3 March 2012
Available online 23 March 2012
Keywords:
Ruthenium
Indenylidene
Dichalcogenoimidodiphosphinate
1. Introduction
solution methods [12,13]. Owing to their electron-donating ability
and steric bulk, [N(R2PE)2]ꢀ can stabilize electron-rich 16e coordin-
Olefin metathesis [1] is widely known as a powerful and versa-
tile tool for the formation of CAC bond in organic synthesis [2] and
polymer chemistry [3]. Ever since the first well-defined ruthenium-
based catalyst discovered by Grubbs and coworkers in 1992 [4],
considerable effort has been devoted to the catalyst modification
in order to get enhanced performance for the transformation of
functionalized olefins [5]. In recent years, ruthenium-indenylidene
based catalysts have attracted great attention due to their
convenient preparation and better stability under harsh conditions
[6]. Ruthenium-indenylidene complexes containing N-heterocyclic
carbenes (NHCs) are the typical examples for metathesis transfor-
mation [7]. Remarkable activity of two new ruthenium-indenylid-
ene complexes with sterically demanding NHC ligand was
observed in ring closing metathesis (RCM) of olefins at low catalyst
loadings [5d].
atively unsaturated Ru(II) complexes [Ru{N(R2PE)2}2(PPh3)] which
are capable of activating H2, SO2 and hydrazine [14]. Herein we
describe syntheses, characterization, and olefin metathesis reactiv-
ity of the ruthenium-indenylidene complexes bearing the dic-
halcogenoimidodiphosphinate ligands.
2. Results and discussion
Treatment
of
[Ru(PPh3)2(Ind)Cl2]
with
the
anionic
dichalcogenoimidodiphosphinate ligands in THF at room tempera-
ture afforded series of 16-electron ruthenium-indenylidene
complexes [Ru(PPh3)(Ind){rE,rE0-R2P(E)NP(E0)R2}Cl] 1aꢀ1f in high
yields, indicating the RuAC(Ind) bond is stable enough towards
the attack of 1 equiv. dichalcogenoimidodiphosphinate ligand
(Scheme 1). Complexes 1aꢀ1f were isolated as air-stable dark red
microcrystals and had good solubility in common organic solvents,
such as THF, diethyl ether, and dichloromethane. However, they
were air-sensitive in solution since colorless crystals of Ph3P@S
and Ph3P@Se, characterized by unit cell determination, were sepa-
rated from the corresponding solution of 1a–1f in air. The 1H NMR
spectra of 1aꢀ1f all showed the characteristic singlet for H-2 at
= 5.78, 5.87, 6.05, 6.11, 5.89(5.80), and 6.11 ppm, respectively (vide
infra). They all shifted upfield compared to [Ru(PPh3)2(Ind)Cl2]
(6.42 ppm). The methyl protons of isopropyl group in complexes
1c and 1d split as dd peaks with coupling constant JHP about
7.0 Hz and JHH about 18.0 Hz, respectively. The 13C NMR spectra
of 1aꢀ1f presented signals around 290 ppm (JPC = 15.0 Hz),
Dichalcogenoimidodiphosphinates, [N(R2PE)2]ꢀ (R = aryl, alkyl;
E = O, S, Se), having been recognized as chalcogenide analogues of
acetylacetonate, can form stable complexes with a range of main
group and transition metal ions [8–11]. These complexes have been
widely used as molecular single-source precursors to thin films,
nanoparticles, or quantum dots by chemical vapor deposition or
⇑
Corresponding authors. Address: Institute of Molecular Engineering and
Applied Chemistry, Anhui University of Technology, Ma’anshan, Anhui 243002, PR
China (Q.-F. Zhang). Tel./fax: +86 555 2312041.
E-mail addresses: jaiquan@ahut.edu.cn (A.-Q. Jia), zhangqf@ahut.edu.cn
(Q.-F. Zhang).
0022-2860/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.molstruc.2012.03.007

28
A.-Q. Jia et al. / Journal of Molecular Structure 1019 (2012) 27–31
PPh3
Cl
PPh3
Ru
PPh3
Ph
Ru
Cl
Cl
R
K[R2P(E)NP(E')R2]
THF, RT
E
Ph
E'
R
P
R
P
N
R
1a-1f
a, R = Ph, E = E' = S; b, R = Ph, E = E' = Se; c, R = iPr, E = E' = S; d, R = iPr, E = E' = Se;
i
e(1), R = Ph, E = S, E' = Se; e(2), R = Ph, E = Se, E' = S; f, R = Pr, E = S, E' = Se
Scheme 1. Synthesis of ruthenium indenylidene complexes 1a–1f.
ascribed to Ru-C1(Ind). Resonances of both PPh3 and
dichalcogenoimidodiphosphinate ligands exhibited in the 31P
NMR spectra of 1aꢀ1f, for example, there were three 31P signals,
appearing at 38.8 (PPh3), 36.0 [P(S)Ph2], 35.2 [P(S)Ph2] ppm in the
31P NMR spectra of 1a. The KBr IR spectra of 1a and 1c showed
the
of
m
(P@S) band at 703 and 699 cmꢀ1, respectively. The frequency
m
(P@Se) band in 1d (528 cmꢀ1) increased compared to the
[N(iPr2PSe)2]ꢀ (520 cmꢀ1) ligand (see Section 3).
It is worthy noting that complex 1e, containing the mixed sul-
fur-selenium ligand, was found to be a mixture of two isomers
1e(1) and 1e(2), as deduced from the NMR data. For example, there
were two singlets of H-2, appeared at d = 5.89 and 5.80 ppm in the
1H NMR spectrum. Additionally, there were six 31P signals in the
31P NMR spectrum, exhibited at 39.2 (PPh3), 38.2 (PPh3), 35.9
(P(S)Ph2), 35.2 (P(S)Ph2), 24.6 (P(Se)Ph2), 22.3 (P(Se)Ph2),
suggesting mixtures of compound 1e. However, complex
[Ru(PPh3)(Ind){rS,rSe-iPr2P(S)NP(Se)iPr2}Cl] 1f supported by bulky
isopropyl substituted mixed donor ligand exists as one isomer only
although we were unable to assign the exact geometry (i.e. cis or
trans). For instance, there is one singlet signal around
d = 6.11 ppm in the 1H NMR spectrum and three signals, showed
at 36.2 (PPh3), 51.4 ((P(Se)iPr2), 63.3 ((P(S)iPr2), in the 31P NMR
spectrum of 1f (see Chart 1).
Single crystals of 1a were obtained by slow diffusion of n-hex-
ane to a concentrate solution of the complex in dichloromethane.
The ORTEP diagram for the structure with selected bond lengths
and angles is shown in Fig. 1. The X-ray crystal structure determi-
nation clearly shows coordination of the Ru center to the indeny-
lidene moiety. The coordination geometry around the ruthenium
center is distorted square pyramidal, with the strongest ligand
(indenylidene) assuming the unique apical site. The square base
is defined by one chloride, the donor atom of the phosphine and
the dithioimidodiphosphinate ligand with the ruthenium center
lying above this plane, the phosphine and chloride being in mutu-
ally cis positions. The six-membered ring RuS2P2N adopts chair-like
conformation. The bond distance of RuAC of 1.860(5) Å in 1a is
Fig. 1. ORTEP drawing of the molecular structure of [Ru(PPh3)(Ind)
(r2S,S-N(Ph2PS)2)Cl] (1a). The hydrogen atoms are omitted for clarity. Selected
bonds (Å) and angles (°): Ru(1)AC(1) 1.860(5), Ru(1)AS(1) 2.406(1), Ru(1)AS(2)
2.384(2), Ru(1)ACl(1) 2.363(2), Ru(1)AP(3) 2.359(1), P(3)ARu(1)ACl(1) 87.84(5),
S(1)ARu(1)AS(2) 99.31(5), C(1)ARu(1)AS(1) 101.03(2), C(1)ARu(1)AP(3)
91.75(15),
C(1)ARu(1)ACl(1)
107.02(16),
P(3)ARu(1)AS(1)
164.48(5),
P(3)ARu(1)AS(2) 88.26(5), Cl(1)ARu(1)AS(1) 80.05(5), Cl(1)ARu(1)AS(2)
157.97(5).
comparable to those in other limited reported ruthenium indeny-
lidene complexes (1.850–1.908 Å) [15]. The average RuAS
bond length in 1a (2.395(2) Å) lies well in other reported ruthe-
nium complexes with dithioimidodiphosphinate ligands, such as
[Ru{N(Ph2PS)2}2(PPh3)] (2.400(2) Å) and [Ru{N(iPr2PS)2}2(PPh3)]
PPh
PPh
3
3
Cl
Cl
Ph
Ph
Ru
Se
Ru
S
Ph
Ph
S
Se
P
P
Ph
Ph
P
P
Ph
Ph
N
N
Ph
1e(1)
Ph
1e(2)
Chart 1. Transformation of complex 1e(1) and 1e(2).

A.-Q. Jia et al. / Journal of Molecular Structure 1019 (2012) 27–31
29
(2.404(2) Å) [14b]. The RuAP bond length in 1a (2.359(1) Å) is
slightly longer than that in [Ru{N(Ph2PS)2}2(PPh3)] (2.218(2) Å).
The RuACl bond length in 1a (2.363(2) Å) is slightly shorter than
those in [Ru(Ind)(PhobCy)2Cl2] (Phob = phosphabicyclononane)
(av. 2.393(2) Å) [15a] and [Ru(Ind)(SIMes)(Py)Cl2] (SIMes = 1,3-
bis(1,3,5-trimethylphenyl)-4,5-dihydroimidazolin-2-ylidene) (av.
2.384(2) Å) [15b]. The bond angle of S(1)ARu(1)AS(2) of
99.31(5)° in 1a is more obtuse than that in [Ru{N(Ph2PS)2}2(PPh3)]
94.34(4)° [14b].
pellets, and elemental analyses for C and H were carried out on an
Elementar III Vario EI analyzer (see Fig. 2).
3.2. Syntheses of complexes [RuCl(PPh3)(Ind){rE,rE0-R2P(E)NR2P(E0)}]
[R = Ph, E = E0 = S (1a); R = Ph, E = E0 = Se (1b); R = iPr, E = E0 = S (1c);
R = iPr, E = E0 = Se (1d); R = Ph, E = S, E0 = Se (1e); R = iPr, E = S, E0 = Se
(1f)]
To a stirred solution of [RuCl2(PPh3)2(Ind)] (44.3 mg, 0.05 mmol)
in 10 mL of THF was added K[R2P(E)NR2P(E0)}] (0.05 mmol) at room
temperature. The mixture was stirred for 12 h and the solvent was
removed in vacuum, the residue was extracted with dichlorometh-
ane and filtered, the filtrate was removed in vacuum and the resi-
due was washed with n-hexane for three times, affording
complexes 1aꢀ1f in quantitive yields.
The catalytic activity of complexes 1aꢀ1f in ring closing
metathesis (RCM) of dienes has been briefly investigated for com-
parison. The catalytic reactions are depicted in Eq. (1).
EtO2C CO2Et
EtO2C CO2Et
5 mol% 1a-1f
ð1Þ
(1)
- C2H4
For 1a, IR (KBr):
m 3054, 1478, 1437, 1151, 1105, 1088, 744, 702,
574, 524 cmꢀ1 31P NMR (CDCl3, 162 MHz): d 38.8 (s, PPh3), 36.0 (s,
.
Complex 1a showed no activity in the RCM at room tempera-
ture or at reflux condition for 6 h in dichloromethane. When the
reaction with 1a was tried in toluene at 80 °C for 2 h, a conversion
of 38% by NMR analysis was found. Other ruthenium indenylidene
complexes 1bꢀ1f were tested under the same conditions. Gener-
P(S)Ph2), 35.2 (s, P(S)Ph2); 1H NMR (CDCl3, 400 MHz): d 8.37–8.35
(m, 1H, ArAH), 8.02–7.97 (m, 2H, ArAH), 7.71–7.60 (m, 5H, ArAH),
7.46–7.01 (m, 34H, ArAH), 6.88–6.83 (m, 2H, ArAH), 5.78 (s, 1H, H-
2); 13C NMR (CDCl3, 100 MHz): d 294.9 (d, JPC = 14.9 Hz, C-1), 145.6
(s), 140.8 (s), 139.2–127.5 (m), 127.1 (s), 117.7 (s). Anal. Calc. for
i
ally, the activities of Pr substituted complexes 1c and 1d (65%,
C57H45ClNP3S2Ru: C 65.98%; H 4.37%; N 1.35%; Found: C, 65.95%;
57%) are more active catalysts than those of the corresponding
phenyl complexes 1a and 1b (48%, 39%), possibly reflecting better
electron donating abilities of iPr towards the ruthenium center. The
activity of ruthenium sulfide complexes 1a (48%) and 1c (65%) is
slightly higher than those of their selenium analogous 1b (39%)
and 1d (57%). Complexes 1e (45%) and 1f (53%) containing mixed
donor ligand also exhibited moderate catalytic behavior. Previ-
ously, Buchmeiser has shown that the replacement of tricyclohex-
ylphosphine to triphenylphosphine has a tremendous effect on the
stability/reactivity of Grubbs’ complexes [16]. When PCy3 was
introduced into the ruthenium-indenylidene complex [RuCl(P-
Ph3)(Ind)(r2S,S-N(iPr2PS)2)] (1c) in situ to replace PPh3, the RCM
catalytic activity was improved to ca. 86%. Overall, compared to
other ruthenium based catalysts [17], the catalytic activity of com-
plexes 1a-f for ring closing metathesis is a little disappointing for
the tested system.
H, 3.39%; N, 1.34%.
For 1b, IR (KBr):
m 3050, 1611, 1487, 1437, 1192, 1097, 744, 690,
524 cmꢀ1 31P NMR (CDCl3, 162 MHz): d 39.1 (s, PPh3), 24.7 (s,
.
P(Se)Ph2), 22.3 (s, P(Se)Ph2); 1H NMR (CDCl3, 400 MHz): d 8.33–
8.32 (m, 1H, ArAH), 7.98–7.93 (m, 2H, ArAH), 7.80–7.75 (m, 2H,
ArAH), 7.73–7.05 (m, 37H, ArAH), 6.90–6.84 (m, 2H, ArAH), 5.87
(s, 1H, H-2); 13C NMR (CDCl3, 100 MHz): d 292.6 (d, JPC = 15.1 Hz,
C-1), 145.2 (s), 140.5 (s), 137.9–127.6 (m), 127.0 (s), 117.8 (s). Anal.
Calc. for C57H45ClNP3Se2Ru: C 60.37%; H 4.00%; N 1.24%; Found: C,
60.34%; H, 4.01%; N, 1.22%.
For 1c, IR (KBr):
m
3058, 2963, 2872, 1623, 1482, 1433, 1188,
1092, 752, 699, 524 cmꢀ1
.
31P NMR (CDCl3, 162 MHz): d 37.6 (s,
PPh3), 59.3 (s, P(S)iPr2), 60.4 (s, P(S)iPr2); 1H NMR (CDCl3,
400 MHz): d 8.58–8.55 (m, 1H, ArAH), 7.78–7.24 (m, 23H, ArAH),
6.05 (s, 1H, H-2), 2.12–1.99 (m, 2H, CH), 1.85–1.78 (m, 1H, CH),
1.62–1.58 (m, 1H, CH), 1.32–0.88 (m, 18H, CH3), 0.78 (dd,
JHH = 17.4 Hz, JHP = 6.8 Hz, 3H, CH3), 0.56 (dd, JHH = 17.8 Hz,
JHP = 6.8 Hz, 3H, CH3); 13C NMR (CDCl3, 100 MHz): d 291.8 (d,
JPC = 15.0 Hz, C-1), 145.1 (s), 141.3 (s), 139.8 (d, JPC = 15.6 Hz),
138.3 (s), 136.7 (s), 135.4 (d, JPC = 15.2 Hz), 132.6–128.1 (m),
126.9 (s), 117.6 (s), 34.3–31.5 (m, CH(CH3)2), 18.2–16.4 (m,
CH(CH3)2). Anal. Calc. for C45H53ClNP3S2Ru: C 59.92%; H 5.93%; N
1.55%; Found: C, 59.95%; H, 5.96%; N, 1.54%.
In summary,
a
series of ruthenium indenylidene
complexes containing dichalcogenoimidodi-phosphinate ligands
i
[R2P(E)NHP(E0)R2] (R = Ph or Pr; E/E0 = S or Se) were synthesized
and well characterized. Complex 1e with the mixed S/Se donor
ligand [Ph2P(S)NP(Se)Ph2]ꢀ was isolated as a mixture of two iso-
mers, while a single isomer was found for complex 1f with
[iPr2P(S)NiPr2P(Se)]ꢀ probably due to steric effect of the bulky iso-
propyl group. The RuAC bond length of 1.860(6) Å in 1a is normal
for the ruthenium-carbene complexes. These complexes exhibited
moderate catalytic activity for the RCM reaction of diethyl
diallylmalonate.
For 1d, IR (KBr):
m
3058, 2959, 2868, 1611, 1482, 1441, 1151,
1093, 1026, 752, 699, 528, 412 cmꢀ1
.
31P NMR (CDCl3, 162 MHz):
d 38.2 (s, PPh3), 51.5 (s, P(Se)iPr2), 50.1 (s, P(Se)iPr2); 1H NMR
(CDCl3, 400 MHz): d 8.52–8.50 (m, 1H, ArAH), 7.57–7.19 (m, 23H,
ArAH), 6.11 (s, 1H, H-2), 2.27–2.24 (m, 1H, CH), 2.10–2.04 (m,
1H, CH), 1.86–1.84 (m, 1H, CH), 1.80–1.72 (m, 1H, CH), 1.31–0.88
(m, 18H, CH3), 0.79 (dd, JHH = 18.0 Hz, JHP = 7.2 Hz, 3H, CH3), 0.57
(dd, JHH = 18.4 Hz, JHP = 7.2 Hz, 3H, CH3); 13C NMR (CDCl3,
100 MHz): d 290.3 (d, JPC = 15.1 Hz, C-1), 145.0 (s), 140.9–128.1
3. Experimental section
3.1. General
All the operations were carried out under pure nitrogen atmo-
sphere using standard Schlenk techniques, solvents were distilled
prior to use. Compounds K[R2P(E)NR2P(E0)}] (R = Ph/iPr; E, E0 = S/
Se) [18] and [Ru(Ind)(PPh3)2Cl2] [19] were prepared according to
modified literature methods. NMR spectra were recorded on a
BrukerALX400 spectrometer operating at 400, 100, and 162 MHz
for 1H, 13C and 31P, respectively. Chemical shifts (d, ppm) were re-
ported with reference to SiMe4 (1H), the residual solvent peak (13C)
and H3PO4 (31P). Infrared spectra (KBr) were recorded on a Perkin-
Elmer 16 PC FT-IR spectrophotometer with the use of pressed KBr
PPh3
2
Cl
1
Ph
Ru
3
4
9
Cl
8
5
PPh3
6
7
Fig. 2. Numbering of ruthenium indenylidene complex [Ru(Ind)(PPh3)2Cl2].

30
A.-Q. Jia et al. / Journal of Molecular Structure 1019 (2012) 27–31
(m), 126.8 (s), 117.6 (s), 34.5–31.1 (m, CH(CH3)2), 18.4–16.6 (m,
CH(CH3)2). Anal. Calc. for C45H53ClNP3Se2Ru: C 54.31%; H 5.37%;
N 1.41%; Found: C, 54.27%; H, 5.39%; N, 1.44%.
in 1a was isotropically refined without hydrogen atoms due to
disorder. Crystallographic data and experimental details for
[Ru(PPh3)(Ind)(r2S,S-N(Ph2PS)2)Cl] (1aꢁhexane) is given in Table 1.
For 1e(1) and 1e(2), IR (KBr):
m 3046, 1482, 1171, 1101, 757,
694, 670, 537, 429 cmꢀ1 31P NMR (CDCl3, 162 MHz): d 39.2 (s,
.
3.4. General procedure for ring closing metathesis reactions
PPh3), 38.2 (s, PPh3), 35.9 (s, P(S)Ph2), 35.2 (s, P(S)Ph2), 24.6 (s,
P(Se)Ph2), 22.3 (s, P(Se)Ph2); 1H NMR (CDCl3, 400 MHz): d 8.37–
8.33 (m, 2H, ArAH), 8.07–6.78 (m, 86H, ArAH), 5.89 (s, 1H, H-2),
Under nitrogen, a Schlenk flask was charged with the substrate
diethyl diallylmalonate (0.5 mmol) and dry dichloromethane or
toluene (5 mL, C = 0.1 M), then pre-catalyst (5 ꢂ 10ꢀ6 mol) was
added. The reaction mixture was magnetically stirred at room tem-
perature or at 80 °C for 2 h. The volatiles were removed under vac-
uum and the crude residue was analyzed by 1H NMR. Product
formation and diene disappearance were monitored by integrating
the allylic methylene peaks. Product formation was confirmed by
comparison with literature NMR data [23].
5.80 (s, 1H, H-2); 13C NMR (CDCl3, 100 MHz):
d 292.2 (d,
JPC = 15.0 Hz, C-1), 145.4 (s), 145.3, 140.9–127.0 (m), 117.7 (s),
117.6 (s). Anal. Calc. for C57H45ClNP3SSeRu: C 63.13%; H 4.18%; N
1.29%; Found: C, 63.10%; H, 4.20%; N, 1.31%.
For 1f, IR (KBr):
m
3058, 2963, 2930, 2868, 1930, 1478, 1441,
1196, 1093, 1030, 752, 703, 549, 528, 512 cmꢀ1
.
31P NMR (CDCl3,
162 MHz): d 36.2 (s, PPh3), 51.4 (s, P(Se)iPr2), 63.3 (s, P(S)iPr2); 1H
NMR (CDCl3, 400 MHz): d 8.53–8.47 (m, 1H, ArAH), 7.70–7.21
(m, 23H, ArAH), 6.11 (s, 1H, H-2), 2.27–2.20 (m, 1H, CH), 2.10–
1.62 (m, 3H, CH), 1.31–0.54 (m, 24H, CH3); 13C NMR (CDCl3,
100 MHz): d 292.2 (d, JPC = 15.1 Hz, C-1), 144.8 (s), 141.3–128.2
(m), 126.8 (d, JPC = 2.2 Hz), 117.6 (s), 34.5–31.0 (m, CH(CH3)2),
18.3–16.4 (m, CH(CH3)2). Anal. Calc. for C45H53ClNP3SSeRu: C
56.99%; H 5.63%; N 1.48%; Found: C, 56.93%; H, 5.69%; N, 1.49%.
Supplementary data
CCDC 831918 contain the supplementary crystallographic data
for complex 1a can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_re-
quest/cif.
3.3. X-ray diffraction measurements
Acknowledgments
Intensity data were collected on a Bruker SMART APEX 2000
This Project was supported by the Natural Science Foundation
of China (20771003) and the Hong Kong Research Grants Council
(Project No. 601708).
CCD diffractometer using graphite-monochromated MoK
a radia-
tion (k = 0.71073 Å). The collected frames were processed with
the software SAINT [20]. The data were corrected for absorption
using the program SADABS [21]. Structures were solved by direct
methods and refined by full-matrix least-squares on F2 using the
SHELXTL software package [22]. All non-hydrogen atoms were re-
fined anisotropically. The positions of all hydrogen atoms were
generated geometrically (Csp3AH = 0.96 and Csp2AH = 0.93), as-
signed isotropic thermal parameters, and allowed to ride on their
respective parent carbon or oxygen atoms before the final
cycle of least-squares refinement. The solvent molecules hexane
References
[1] (a) R.H. Grubbs, Handbook of Metathesis, vols. 1-3, Wiley-VCH, Weinheim,
2003;
(b) RR. Schrock, Angew. Chem. Int. Ed. 45 (2006) 3748;
(c) R.H. Grubbs, Angew. Chem. Int. Ed. 45 (2006) 3760.
[2] (a) T.J. Donohoe, L.P. Fishlock, P.A. Procopiou, Chem. Eur. J. 14 (2008) 5716;
(b) W.A.L. van Otterlo, C.B. de Koning, Chem. Rev. 109 (2009) 3743;
(c) A. Gradillas, J. Perez-Castells, Angew. Chem. Int. Ed. 45 (2006) 6086.
[3] M.R. Buchmeiser, Chem. Rev. 100 (2000) 1565.
[4] S.T. Nguyen, L.K. Johnson, R.H. Grubbs, J.W. Ziller, J. Am. Chem. Soc. 114 (1992)
3974.
[5] (a) C.E. Diesendruck, E. Tzur, N.G. Lemcoff, Eur. J. Inorg. Chem. (2009) 4185;
(b) C. Samojłowicz, M. Bieniek, K. Grela, Chem. Rev. 109 (2009) 3708;
(c) G.C. Vougioukalakis, R.H. Grubbs, Chem. Rev. 110 (2010) 1746;
(d) C.A. Urbina-Blanco, A. Leitgeb, C. Slugovc, X. Bantreil, H. Clavier, A.M.Z.
Slawin, S.P. Nolan, Chem. Eur. J. 17 (2011) 5045.
Table 1
Crystallographic data and experimental details for [Ru(P-
Ph3)(Ind)(r2S,S-N(Ph2PS)2)Cl] (1aꢁhexane).
Complex
1aꢁHexane
C66H58NClP3S2Ru
[6] (a) R. Castarlenas, C. Vovard, C. Fischmeister, P.H. Dixneuf, J. Am. Chem. Soc.
128 (2006) 4079;
Empirical formula
Formula weight
Crystal system
a (Å)
b (Å)
c (Å)
(b) M. Bieniek, A. Michrowska, D.L. Usanov, K. Grela, Chem. Eur. J. 14 (2008)
806;
(c) H. Clavier, C.A. Urbina-Blanco, S.P. Nolan, Organometallics 28 (2009) 2848;
(d) A. Antonucci, M. Bassetti, C. Bruneau, P.H. Dixneuf, C. Pasquini,
Organometallics 29 (2010) 4524;
1158.68
Triclinic
12.7779(19)
13.7203(19)
17.624(3)
75.478(2)
88.514(2)
64.692(2)
2692.3(7)
P ꢀ 1
(e) X. Bantreil, T.E. Schmid, R.A.M. Randall, A.M.Z. Slawin, C.S.J. Cazin, Chem.
Commun. 46 (2010) 7115.
a
(°)
b (°)
[7] (a) F. Boeda, H. Clavier, S.P. Nolan, Chem. Commun. (2008) 2726;
(b) S.P. Nolan, H. Clavier, Chem. Soc. Rev. 39 (2010) 3305.
[8] I. Haiduc, in: J.A. McCleverty, T.J. Meyer (Eds.), Comprehensive Coordination
Chemistry II, vol. 1, Elsevier Pergamon, Amsterdam, 2004, p. 323.
[9] A.M.Z. Slawin, M.B. Smith, J.D. Woollins, J. Chem. Soc. Dalton Trans. (1996)
3659.
c
(°)
V (Å3)
Space group
Z
2
Dcalc (g cmꢀ3
)
1.429
[10] P. Sekar, J.A. Ibers, Inorg. Chim. Acta 359 (2006) 2751.
[11] W.-M. Cheung, W.-H. Chiu, I.D. Williams, W.-H. Leung, Eur. J. Inorg. Chem.
(2009) 792.
[12] A. Panneerselvam, M.A. Malik, M. Afzaal, P. O’Brien, M. Helliwell, J. Am. Chem.
Soc. 130 (2008) 2420.
[13] D.J. Crouch, P. O’Brien, M.A. Malik, P.J. Skabara, S.P. Wright, Chem. Commun.
(2003) 1454.
[14] (a) W. Cheung, Q.-F. Zhang, C.-Y. Lai, I.D. Williams, W.-H. Leung, Polyhedron 26
(2007) 4631;
Temperature (K)
296(2)
1340
0.552
16,737
11,855
0.0582
0.0593, 0.0969
0.0806, 0.1257
676
F(000)
l(MoK
a
) (mmꢀ1
)
Total refln
Independent refln
Rint
R1a, wR2b (I > 2
r
(I))
R1, wR2 (all data)
Parameter
GoFc
(b) W.-H. Leung, H. Zheng, J.L.C. Chim, J. Chan, W.-T. Wong, I.D. Williams,
Dalton Trans. (2000) 423;
0.829
(c) Q.F. Zhang, H. Zheng, W.Y. Wong, W.T. Wong, W.H. Leung, Inorg. Chem. 39
(2000) 5255.
[15] (a) G.S. Forman, R.M. Bellabarba, R.P. Tooze, A.M.Z. Slawin, R. Karch, R. Winde, J
Organomet. Chem. 691 (2006) 5513;
a
b
c
R1 =
wR2 ¼ ½
GoF = [
R
||Fo|–|Fc||/
R
|Fo|.
2
2
1=2
R
wðjF2oj ꢀ jF2c jÞ =
R
wjF2oj ꢃ
.
R
w(|Fo|–|Fc|)2/(Nobs–Nparam)]1/2
.

A.-Q. Jia et al. / Journal of Molecular Structure 1019 (2012) 27–31
31
(b) D. Burtscher, C. Lexer, K. Mereiter, R. Winde, R. Karch, C. Slugovc, J. Polym.
Sci. Polym. Chem. Ed. 46 (2008) 4630.
[19] A. Fürstner, O. Guth, A. Düffels, G. Seidel, M. Liebl, B. Gabor, R. Mynott, Chem.
Eur. J. 7 (2001) 4811.
[16] Michael R. Buchmeiser, Chem. Rev. 100 (2000) 1565.
[17] (a) I.C. Stewart, T. Ung, A.A. Pletnev, J.M. Berlin, R.H. Grubbs, Y. Schrodi, Org.
Lett. 9 (2007) 1589;
[20] G.M. Sheldrick, SADABS, University of Göttingen, Germany, 1996.
[21] SMART and SAINT+ for Windows NT Version 6.02a; Bruker Analytical X-ray
Instruments Inc.: Madison, WI, 1998.
(b) B.D. Clercq, Francis. Verpoort, Tetrahedron Lett. 43 (2002) 9101;
(c) D. Rix, H. Clavier, Y. Coutard, L. Gulajski, K. Grela, M. Mauduit, J. Organomet.
Chem. 691 (2006) 5397.
[22] (a) G.M. Sheldrick, SHELXTL Software Reference Manual, Version 5.1, Bruker
AXS Inc., Madison, WI, 1997;
(b) G.M. Sheldrick, Acta Crystallogr. A64 (2008) 112.
[18] D. Cupertino, D.J. Birdsall, A.M.Z. Slawin, J.D. Woollins, Inorg. Chim. Acta 290
(1999) 1.
[23] E.L. Dias, S.T. Nguyen, R.H. Grubbs, J. Am. Chem. Soc. 119 (1997) 3887.