Reactivity of the 16e (p-cymene)Ru half-sandwich complex containing a chelating 1,2-dicarba-closo-dodecaborane-1,2-dithiolate ligand towards diynes

Article abstract of DOI:10.1039/c1dt10291e

The reactions of the 16e half-sandwich complex (p-cymene)Ru(S ₂C₂B₁₀H₁₀) (Ru16e) with 1,4-diethynylbenzene (L1), 3′,6-diethynyl-1,1′-binaphthyl-2, 7′-diyl diacetate (L2), 2-bromo-5-ethynylthiophene (L3) and 2,5-diethynylthiophene (L4) lead to 18e mononuclear complexes (p-cymene)Ru(S₂C₂B₁₀H₉)(H ₂CCPhCCH) (1), (p-cymene)Ru(S₂C₂B ₁₀H₉)[H₂CC(C₂₄H₁₆O ₄)CCH] (2), (p-cymene)Ru(S₂C₂B ₁₀H₉) [H₂CC(C₄H₂S)Br] (3) and (p-cymene)Ru(S₂C₂B₁₀H₉) [H ₂CC(C₄H₂S)CCH] (4), respectively. In all of them, metal-induced B-H activation has occurred, which leads to a stable Ru-B bond, and the structures take a cisoid arrangement. Only in the case of L4, the binuclear complexes [(p-cymene)Ru(S₂C₂B₁₀H ₉)]₂[H₂CC(C₄H₂S)CCH ₂] (5a and 5b) are observed, which are conformational isomers generated by the differing orientations of the p-cymene unit. 4 can be readily converted to the complex (p-cymene)Ru(S₂C₂B ₁₀H₉)[H₂CC(C₄H₂S) COCH₃] (6) in the presence of silica and H₂O. All of these products 1-6 were characterized by NMR, IR, elemental analysis and mass spectrometry. The structures of 1, 3, and 5a were also determined by single-crystal X-ray diffraction analysis.

Full text of DOI:10.1039/c1dt10291e

View Article Online / Journal Homepage / Table of Contents for this issue
Dynamic Article Links
Dalton
Transactions
Cite this: Dalton Trans., 2011, 40, 6992
www.rsc.org/dalton
PAPER
Reactivity of the 16e (p-cymene)Ru half-sandwich complex containing a
chelating 1,2-dicarba-closo-dodecaborane-1,2-dithiolate ligand towards
diynes†
Zhi-Wei Xu, Lei Han, Cheng Ji, Rui Zhang, Xu-Jie Shen and Hong Yan*
Received 21st February 2011, Accepted 26th April 2011
DOI: 10.1039/c1dt10291e
The reactions of the 16e half-sandwich complex (p-cymene)Ru(S2C2B10H10) (Ru16e) with
1,4-diethynylbenzene (L1), 3¢,6-diethynyl-1,1¢-binaphthyl-2,7¢-diyl diacetate (L2),
2-bromo-5-ethynylthiophene (L3) and 2,5-diethynylthiophene (L4) lead to 18e mononuclear complexes
(p-cymene)Ru(S2C2B10H9)(H2CCPhC CH) (1), (p-cymene)Ru(S2C2B10H9)[H2CC(C24H16O4)C CH]
(2), (p-cymene)Ru(S2C2B10H9) [H2CC(C4H2S)Br] (3) and (p-cymene)Ru(S2C2B10H9)
[H2CC(C4H2S)C CH] (4), respectively. In all of them, metal-induced B–H activation has occurred,
which leads to a stable Ru–B bond, and the structures take a cisoid arrangement. Only in the case of
L4, the binuclear complexes [(p-cymene)Ru(S2C2B10H9)]2[H2CC(C4H2S)CCH2] (5a and 5b) are
observed, which are conformational isomers generated by the differing orientations of the p-cymene
unit. 4 can be readily converted to the complex (p-cymene)Ru(S2C2B10H9)[H2CC(C4H2S)COCH3] (6) in
the presence of silica and H2O. All of these products 1–6 were characterized by NMR, IR, elemental
analysis and mass spectrometry. The structures of 1, 3, and 5a were also determined by single-crystal
X-ray diffraction analysis.
Introduction
On the basis of the varying reaction chemistry of 16e transition
metal (Co, Rh, Ir, Ru, Os) half-sandwich complexes containing
a chelating 1,2-dicarba-closo-dodecaborane-1,2-dithiolate ligand,
the conversions to their 18e congeners have been extensively
investigated.1–10 They could be used as precursors for the synthesis
of multi-metal clusters, in which metal–metal bonds are built
up.1,2 Metal centers coordinated by Lewis base ligands have led
to mononuclear,3,4 binuclear,4b,5 and multinuclear6 complexes. The
reactivity towards an alkyne has also been focused on, affording
various products, such as from alkyne insertion,7–10 alkyne dimer-
ization at one M–E bond (E = S, Se)8–10 and compounds bearing
a metal–boron bond8,9 or a carbon–boron bond.8–11 However, the
reaction chemistry of these 16e complexes with diyne ligands has
not been studied.
On the other hand, various binuclear complexes of Mn,12 U,13
Pt,14 Au,15 Ru16 bearing ligands other than the 1,2-dicarba-closo-
dodecaborane-1,2-dithiolate ligand have also been synthesized
through the reactions of the corresponding precursors with diynes,
in which the metal centers are mostly coordinated by a s-bond
leading to an approximately linear structure (Scheme 1). If a metal
Scheme 1 Previous results from the reactions of some metal compounds
with 1,4-diethynylbenzene.12–17
center could activate an X–H bond, or has a coordinated H atom,
an alkynyl group could be converted to an alkenyl group that binds
to a metal center by a s-bond (Scheme 1).17 In this paper, we report
on the reactions of the 16e complex (p-cymene)Ru(S2C2B10H10)
(Ru16e) with diynes (L1, L2, L4), in expectation of obtaining new
types of binuclear complexes.
Results and discussion
The reaction of Ru16e and L1 in a ratio of 2 : 1 at ambient
temperature leads to a sole product, 1, in a yield of 83%, as shown
in Scheme 2. The solid-state structure (Fig. 1) shows that the B(3)–
H bond was activated and a new Ru–B bond generated. The bond
State Key Laboratory of Coordination Chemistry, School of Chemistry and
Chemical Engineering, Nanjing University, Jiangsu, 210093, China. E-mail:
hyan1965@nju.edu.cn; Fax: +86-25-83314502; Tel: +86-25-83686724
† CCDC reference numbers 806363–806365. For crystallographic data in
CIF or other electronic format see DOI: 10.1039/c1dt10291e
˚
˚
length of Ru–B(3) (2.099 A) is close to those (~2.1 A) of the similar
ruthenium compounds previously published.8c,9e One hydrogen
6992 | Dalton Trans., 2011, 40, 6992–6997
This journal is
The Royal Society of Chemistry 2011
©

View Article Online
Table 1 13C data of 1–6
C2B10H10
p-cymene
Ph, nalphene or thiophene
Ru–CH2
Ru–C–S Other
1
2
93.87, 102.44
18.29, 22.16, 23.31, 29.78,
96.61, 99.22, 101.17,
104.94, 109.18, 121.08
18.34, 22.24, 22.93, 30.84,
95.78, 99.25, 100.91,
121.01, 124.92, 132.35, 145.07
35.25
83.31
85.15
77.85 (C CH), 84.42 (C CH)
94.03, 102.77
119.49, 122.64, 122.75, 123.05,
123.54, 126.09, 126.18, 126.37,
126.42, 129.33, 129.40, 129.47,
129.54, 131.04, 131.56, 132.41,
141.48, 146.90, 147.62, 150.23
110.30, 122.84, 130.02, 151.45
35.40
77.99 (C CH), 83.49 (C CH),
20.54 (CH3 of Ac), 21.00 (CH3 of Ac),
168.94 (C O), 169.02 (C O)
104.54, 108.60, 122.49
3
93.05, 102.04
93.16, 102.14
92.81, 101.48
92.42, 101.20
92.99, 101.89
18.70, 21.83, 23.60, 31.50,
97.56, 99.58, 101.67,105.67,
109.13, 121.38,
18.71, 21.75, 23.66, 31.53,
97.60, 99.95, 101.81,
105.91, 108.73, 119.47
18.62, 22.13, 23.28, 31.28,
97.03, 99.07, 101.75,
105.12, 109. 34, 121.77
18.71, 21.85, 23.54, 31.40,
97.14, 99.74, 102.12,
36.87
37.16
36.34
36.83
37.69
80.67
80.36
80.98
80.62
79.78
4
121.56, 122.92, 133.65, 151.86
125.92, 146.33
77.12 (C CH), 81.90 (C CH)
5a
5b
6
126.85, 148.29
105.39, 107.97, 122.06
18.78, 21.34, 23.86, 31.57,
98.03, 100.63, 102.31,
106.42, 108.15, 121.99
124.75, 133.40, 140.57, 159.09
26.35 (O C–CH3), 190.41 (C O)
Scheme 2 Reactions of Ru16e with L1, L2, L3 and L4.
Fig. 1 The molecular structure of 1. Thermal ellipsoids are depicted
at 30% probability. All of the hydro◦gen atoms are omitted for clarity.
˚
Selected bond lengths (A) and angles ( ): Ru(1)–C(3) 2.159(4), Ru(1)–C(4)
1
The NMR data support this solid-state structure. In the H
NMR spectrum, two characteristic doublets at 2.61 and 3.93 ppm
and the singlet at 3.13 ppm are designated to the Ru–CH2 unit and
the retained C CH unit of the originally used dyine, respectively.
The regio- and stereochemistry of the alkyne addition, as shown in
Scheme 2, was assumed according to the proton chemical shifts of
the Ru–CH2 unit. The small value (3 Hz) of the geminal coupling
constant 2J (1H,1H) is typical of terminal alkenes coordinated to
metal centres. The 13C NMR data indicate the coordinated alkenyl
carbons at 35.25 ppm for C3 and 83.31 ppm for C4, as well as the
unreacted alkynyl carbons at 77.85 ppm for C12 and 84.42 ppm
for C11, as confirmed by 2D 13C–1H correlation experiments (see
Table 1). The 11B NMR signal of the boron atom linked to the
metal is broader and identified as -12.0 ppm by comparison of the
1H coupled and 1H decoupled 11B NMR spectra.
2.163(4), Ru(1)–B(3) 2.099(4), Ru(1)–S(2) 2.4298(11), C(1)–C(2) 1.699(6),
C(1)–S(1) 1.772(4), C(2)–S(2) 1.780(4), C(3)–C(4) 1.403(6), C(4)–C(5)
1.495(5), C(4)–S(1) 1.821(4), C(11)–C(12) 1.175(6), C(3)–Ru(1)–C(4)
37.89(15), B(3)–Ru(1)–S(2) 71.58(12), C(3)–C(4)–C(5) 123.2(4),
C(3)–C(4)–S(1) 117.7(3), S(1)–C(4)–C(5) 109.4(3), C(1)–S(1)–C(4)
102.26(18), Ru(1)–S(2)–C(2) 88.30(14).
atom was transferred from carborane to the terminal carbon atom
of the alkyne to generate alkene coordination, as shown by the
˚
C(3)–C(4) bond length of 1.403 A. Note that only one C C bond
is involved in the reaction and the other remains unreacted, as
˚
seen from the C(11)–C(12) bond length of 1.175 A. The C(1)–
˚
C(2) bond length (1.699 A) of the carborane is in the typical
range of the known o-carborane derivatives of 1.62–1.70 A.18 The
˚
2
X-ray structural analysis suggests that the S-h -(R1)C C and
A previous study of the reaction of Ru16e with ethynylbenzene
showed that a cisoid-arrangement could be converted to a transoid-
arrangement if it was heated in boiling CHCl3,9 but 1 shows no
conversion, even when heated in boiling toluene, reflecting the
stable cisoid-structure and the stable Ru–B bond. Moreover, the
the C1–B3(M) bonds now point in the same direction (cisoid-
arrangement) in the coordination sphere of the ruthenium atom,
which is analogous to the product from the reaction of Ru16e and
ethynylbenzene.9
This journal is
The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 6992–6997 | 6993
©

View Article Online
terminal alkynyl unit with potential reactivity in 1 does not further
react with excess Ru16e to generate the expected binuclear species.
The complexes 2, 3, and 4 were prepared following the same
procedure, as seen in Scheme 2, and they possess the same
structural type as 1, as established by spectroscopic data. Note
that, for comparison, we further performed the reaction of Ru16e
with monoyne L3. Their 1H NMR data are similar. For example,
the two Ru–CH2 proton signals appear at 2.67/4.06, 2.55/3.74
and 2.59/3.79 ppm, with a coupling constant of 3 Hz in 2, 3
and 4, respectively. The 13C NMR data summarized in Table
1 also provide powerful evidence. The 13C values of carborane,
p-cymene and the Ru–CH2 units are very close. Also, the 11B
NMR spectra show the typical pattern of signals for o-carborane
derivatives.19 The X-ray structural analysis of 3 (Fig. 2) suggests
Fig. 3 The molecular structure of 5a. Thermal ellipsoids are de-
a cisoid-arrangement as well. On the basis of our previous study,9
picted at 30% probability. All of the hydrogen atoms are omitted
◦
˚
for clarity. Selected bond lengths (A) and angles ( ): Ru(1)–C(3)
2.147(6), Ru(1)–C(4) 2.171(6), Ru(1)–B(3) 2.105(6), Ru(1)–S(2) 2.4203(17),
C(1)–C(2) 1.708(7), C(1)–S(1) 1.773(6), C(2)–S(2) 1.761(5), C(3)–C(4)
1.397(8), C(4)–C(5) 1.473(7), C(4)–S(1) 1.814(6), C(5)–S(3) 1.734(5),
C(5)–C(6) 1.359(7), C(6)–C(6A) 1.410(7), C(3)–Ru(1)–C(4) 37.8(2),
B(3)–Ru(1)–S(2) 71.75(17), C(3)–C(4)–C(5) 122.4(5), C(3)–C(4)–S(1)
119.2(4), C(1)–S(1)–C(4) 101.5(3), Ru(1)–S(2)–C(2) 88.14(18).
2
it could be safely assumed that in 2 and 4 the S-h -(Rn)C
C
and the C–B(M) bonds occupy a cisoid position, parallel to 1
and 3. Additionally, 2 and 4 do not react with excess Ru16e to
give binuclear complexes. The cisoid-arrangement in 2–4 does not
convert to the transoid-arrangement, even when it is heated in
boiling toluene, again indicating the stability of the Ru–B bonds,
since such a rearrangement requires the cleavage of a Ru–B bond
and then its regeneration.
and 7.43 ppm in 5b indicate that the two protons in thiophene are
in the same magnetic environment. The two pairs of doublets at
2.54/3.83 and 2.55/3.63 ppm are recognized as Ru–CH2 in 5a and
5b, respectively. The subtle differences between the 1H data of 5a
and 5b further demonstrate that they are not geometrical isomers
1
of the cisoid and transoid structures, since the H difference in
the corresponding chemical shifts of the M–CH2 unit can reach
up to 1 ppm for the cisoid- and transoid-arrangements.9 Thus, the
coexistence of 5a and 5b is attributed to the hindered rotation of the
p-cymene ligand. This happened in our previous system.9b Note
that 5a and 5b cannot be interconverted and cannot be converted
to a transoid-arrangement if heated at 110 ◦C.
Thus, on the basis of the three typical diynes selected in this
reaction system, the results indicate that the ligand type plays a
key role in the generation of a binuclear complex. The reactivity
of diyne ligands in the formation of a binuclear complex is
determined by the electronic effect, rather than the steric hindrance
or rigidity of the diynes.
The conversion of 4 to 6 (Scheme 3) was observed in the presence
of silica and H2O. Here, silica seems to assist the reaction, even
though the conversion from an alkynyl group to an acetyl group
mediated by acid20 or metal21 has been reported. Unfortunately,
suitable single crystals for X-ray analysis were not obtained, but
the spectroscopic data support the proposed structure. In the 1H
NMR spectrum the characteristic singlet at 2.51 ppm assigned
to O C–CH3 has replaced the singlet at 3.38 ppm assigned to
Fig. 2 The molecular structure of 3. Thermal ellipsoids are depicted at
30% probability. All of the hydrogen atoms are omitted for clarity. Selected
◦
˚
bond lengths (A) and angles ( ): Ru(1)–C(3) 2.168(6), Ru(1)–C(4) 2.178(6),
Ru(1)–B(3) 2.134(7), Ru(1)–S(2) 2.4251(17), C(1)–C(2) 1.708(9), C(1)–S(1)
1.758(7), C(2)–S(2) 1.769(7), C(3)–(4) 1.416(8), C(4)–C(5) 1.482(9),
C(4)–S(1) 1.808(6), C(3)–Ru(1)–C(4) 38.0(2), B(3)–Ru(1)–S(2) 71.4(2),
C(3)–C(4)–C(5) 121.6(6), C(3)–C(4)–S(1) 118.8(5), C(1)–S(1)–C(4)
101.8(3), Ru(1)–S(2)–C(2) 88.5(2).
C
CH in 4. Also, in the 13C NMR spectrum, peaks at 26.35 and
Apart from 4, the 1H spectrum indicates that a pair of fluxional
isomers 5a and 5b are generated from the reaction of Ru16e and
L4, owing to rotation of the p-cymene ligand about the metal-
ring-centroid axis. Fortunately, we obtained good-quality single
crystals of 5a by recrystallization, but failed to obtain crystals
of 5b. The X-ray structural analysis (Fig. 3) shows that 5a is the
binuclear and symmetric structure and both of the two pairs of
2
S-h -(R4)C C and C–B(M) bonds occupy a cisoid position.
1
The H NMR spectrum shows a ratio of 5 : 1 of 5a and 5b in
solution at ambient temperature. The singlets at 7.06 ppm in 5a
Scheme 3 The conversion of 4 to 6.
This journal is The Royal Society of Chemistry 2011
6994 | Dalton Trans., 2011, 40, 6992–6997
©

View Article Online
190.41 ppm are attributed to O C–CH3, instead of the terminal
alkynyl group at 77.12 and 81.90 ppm in 4. Moreover, the closer
related NMR data in 6, compared to those of compounds 1–5
imply a cisoid-arrangement as well. A vibration band at 1635 cm-1
was observed for the carbonyl group in the IR spectrum and the
elemental analysis shows that the measured data fit the calculated
ones well. Thus, we deduced the structure of 6, as presented in
Scheme 3.
7 Hz, 3H, p-cymene CH–CH3), 2.11 (s, 3H, p-cymene CH3), 2.55
(sp, J = 7 Hz, 1H, p-cymene CH–(CH3)2), 2.61 (d, J = 3 Hz, 1H,
Ru–CH2), 3.13 (s, 1H, C CH), 3.93 (d, J = 3 Hz, 1H, Ru–CH2),
5.35, 5.37, 5.52, 5.62 (d, J = 6 Hz, 4H, p-cymene CH), 7.36 (d, J =
8.5 Hz, 2H, CH), 7.89 (d, J = 8.5 Hz, 2H, CH).11B NMR (CDCl3):
d -1.9 (2B), -2.7 (3B), -7.5 (1B), -8.4 (1B), -10.1 (1B), -10.8 (1B),
-12.0 (1B, Ru–B). EI–MS (70 eV): m/z 512 (M+, 50%). IR (KBr):
n (cm-1) 2582 (B–H). Anal. calcd for C20H28S3B10Ru: C, 41.86; H,
4.92. Found: C, 41.71; H, 5.04%.
◦
1
2: yellow solid; yield, 68.2 mg, 82%; m.p. = 168 C. H NMR
(CDCl3): d 0.88 (d, J = 7 Hz, 3H, p-cymene CH–CH3), 1.26 (d,
J = 7 Hz, 3H, p-cymene CH–CH3), 1.90 (s, 3H, CH3–C O),
1.95(s, 3H, CH3–C O), 2.04 (s, 3H, p-cymene CH3), 2.47 (sp,
J = 7 Hz, 1H, p-cymene CH–(CH3)2), 2.67 (d, J = 3 Hz, 1H, Ru–
CH2), 3.15 (s, 1H, C CH), 4.06 (d, J = 3 Hz, 1H, Ru–CH2), 5.57,
5.58, 5.59, 5.65 (d, J = 6 Hz, 4H, p-cymene CH), 6.99, 7.04, 7.09,
7.30, 7.41, 7.44, 7.68, 7.78, 7.97, 8.50 (10H, naphthalene ring).11B
NMR (CDCl3): d -4.0 (5B), -9.4 (3B), -12.2 (2B) (overlapping
signals without assignment of Ru–B). EI–MS (70 eV): m/z 832
(M+, 15%). IR (KBr): n (cm-1) 1648 (C O), 2577 (B–H). Anal.
calcd for C40H46B10RuO2S2: C, 57.74; H, 5.57. Found: C, 57.50; H,
5.46%.
Conclusions
The 16e complex (p-cymene)Ru(S2C2B10H10) behaves similarly
towards selected diynes L1, L2 and L4 to give rise to mononuclear
products, in which selective B–H activation at the carborane has
occurred and a stable Ru–B bond is present. Unexpectedly, the
reactivity of the second alkynyl group of the resulting mononuclear
products is exterminated or tremendously inhibited, no matter
whether the diyne used is rigid or not. The electronic effect, rather
than steric factors, of the diynes plays a key role in the generation
of binuclear complexes. This study enriches the reaction chem-
istry of 16e transition-metal half-sandwich complexes containing
a chelating 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolate
ligand.
◦
1
3: yellow solid; yield 53.6 mg, 86%; m.p. = 132 C. H NMR
(CDCl3): d 1.06 (d, J = 7 Hz, 3H, p-cymene CH–CH3), 1.20 (d, J =
7 Hz, 3H, p-cymene CH–CH3), 2.22 (s, 3H, p-cymene CH3), 2.55
(d, J = 3 Hz, 1H, Ru–CH2), 2.66 (sp, J = 7 Hz, 1H, p-cymene CH–
(CH3)2), 3.74 (d, J = 3 Hz, 1H, Ru–CH2), 5.43, 5.46, 5.73, 5.81 (d,
J = 6 Hz, 4H, p-cymene CH), 6.79 (d, J = 4 Hz, 1H, thiophene
CH), 7.12 (d, J = 4 Hz, 1H, thiophene CH).11B NMR (CDCl3):
d -1.7 (4B), -3.4 (1B, JB–H = 120 Hz), -7.5 (2B), -8.3 (1B), -10.0
(1B), -10.7 (1B, Ru–B). EI–MS (70 eV): m/z 441 ([M–L3]+, 61%),
186 (L3+, 5%). IR (KBr): n (cm-1) 2582 (B–H). Anal. calcd for
C18H27B10BrRuS3·CH2Cl2: C, 31.98; H, 4.10. Found: C, 32.25; H,
4.16%.
Experimental
All manipulations were performed under an argon atmosphere us-
ing standard Schlenk techniques. Solvents were dried by refluxing
over sodium (petroleum ether, ether, and THF) or calcium hydride
(dichloromethane) under nitrogen and then distilled prior to use.
[(p-cymene)RuCl2]2,22 L2,23 L324 and L424 were prepared according
to the literature methods. n-Butyllithium (2.0 M in cyclohexane,
Aldrich), 2,5-dibromothiophene (J&K) and L1 (Aldrich) were
used as received, without further purification. Elemental analysis
was performed in an Elementar Vario EL III elemental analyzer.
NMR measurements were obtained on a Bruker DRX-500
◦
1
4: yellow solid; yield, 20.1 mg, 35%; m.p. = 156 C. H NMR
(CDCl3): d 1.03 (d, J = 7 Hz, 3H, p-cymene CH–CH3), 1.19 (d, J =
7 Hz, 3H, p-cymene CH–CH3), 2.21 (s, 3H, p-cymene CH3), 2.59
(d, J = 3 Hz, 1H, Ru–CH2), 2.61 (sp, J = 7 Hz, 1H, p-cymene CH–
(CH3)2), 3.38 (s, 1H, C CH), 3.79 (d, J = 3 Hz, 1H, Ru–CH2),
5.43, 5.45, 5.71, 5.83 (d, J = 6 Hz, 4H, p-cymene CH), 7.08 (d, J = 4
Hz, 1H, thiophene CH), 7.32 (d, J = 4 Hz, 1H, thiophene CH).11B
NMR (CDCl3): d -1.5 (4B), -3.4 (1B, JB–H = 125 Hz), -7.5 (2B),
-8.4 (1B), -10.1 (1B), -10.8 (1B, Ru–B). EI–MS (70 eV): m/z 441
([M–L4]+, 2%), 132 (L4+, 1%). IR (KBr): n (cm-1) 2580 (B–H).
Anal. calcd for C20H28S3B10Ru: C, 41.86; H, 4.92. Found: C, 41.71;
H, 5.04%.
1
spectrometer. H NMR and 13C NMR spectra were reported in
1
ppm with respect to CHCl3/CDCl3 (d H = 7.24, d 13C = 77.0)
and 11B NMR spectra were reported in ppm with respect to
external Et2O·BF3 (d 11B = 0). The IR spectra were recorded on a
Bruker Tensor 27 spectrophotometer with KBr pellets in the 4000–
400 cm-1 region. The mass spectra were recorded on Micromass
GC-TOF for EI-MS (70 eV) or Finnigan MAT TSQ7000 for
ESI-MS. Matrix-assisted laser desorption/ionization (MALDI) in
linear time-of-flight (TOF) mass spectrometry (MS) was recorded
in a Bruker autoflex TOF/TOF equipped with an acquisition
operation mode of reflector and signal averaging of 30 laser shots.25
5a and 5b: red solid; yield, 57.9 mg, 57%. 5a: m.p. = 141 ◦C. 1H
NMR (CDCl3): d 1.04 (d, J = 7 Hz, 6H, p-cymene CH–CH3), 1.17
(d, J = 7 Hz, 6H, p-cymene CH–CH3), 2.22 (s, 6H, p-cymene CH3),
2.54 (d, J = 3 Hz, 2H, Ru–CH2), 2.61 (sp, J = 7 Hz, 2H, p-cymene
CH–(CH3)2), 3.83 (d, J = 3 Hz, 2H, Ru–CH2), 5.47, 5.51, 5.70, 5.80
(d, J = 6 Hz, 8H, p-cymene CH), 7.06 (s, 2H, thiophene CH).11B
NMR (CDCl3): d -1.4 (5B), -7.4 (3B), -10.0 (2B) (overlapping
signals without assignment of Ru–B). MALDI-TOF MS: (m/z)
1016 ([M+H]+, 13%). IR (KBr): n (cm-1) 2581 (B–H). Anal. Calcd
for C32H52B20Ru2S5·2CH2Cl2: C, 34.45; H, 4.76. Found: C, 35.21;
H, 4.66%. 5b: 1H NMR (CDCl3): d 1.01 (d, J = 7 Hz, 6H, p-cymene
CH–CH3), 1.18 (d, J = 7 Hz, 6H, p-cymene CH–CH3), 2.23 (s, 6H,
p-cymene CH3), 2.55 (d, J = 3 Hz, 2H, Ru–CH2), 2.61 (sp, J = 7
General synthesis of 1–5
The alkyne (0.1 mmol) was added to a blue solution of (p-
cymene)Ru(S2C2B10H10) (88.3 mg, 0.2 mmol). The resulting mix-
ture was stirred overnight at ambient temperature. The color
changed to brown or red-brown. After removal of the solvent, the
residue was chromatographed on silica gel. Elution with petroleum
ether/CH2Cl2 gave the corresponding products. The yields are
calculated based on the ligand.
◦
1
1: yellow solid; yield, 47.5 mg, 83%; m.p. = 145 C. H NMR
(CDCl3): d 0.99 (d, J = 7 Hz, 3H, p-cymene CH–CH3), 1.14 (d, J =
This journal is
The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 6992–6997 | 6995
©

View Article Online
Table 2 Crystallographic data for 1, 3 and 5a
1
3
5a
Chemical formula
Crystal size/mm
Formula weight
T/K
C22H30B10RuS2
0.30 ¥ 0.26 ¥ 0.24
567.75
C18H27B10BrRuS3·CH2Cl2
0.11 ¥ 0.10 ¥ 0.09
713.58
C32H52B20Ru2S5·2CH2Cl2
0.12 ¥ 0.11 ¥ 0.10
1185.23
291(2)
293(2)
293(2)
˚
˚
˚
radiation
Mo-Ka(0.71073 A)
Mo-Ka(0.71073 A)
monoclinic
P21/c
Mo-Ka(0.71073 A)
Crystal system
triclinic
triclinic
¯
¯
P1
Space group
P1
˚
a/A
8.6951(7)
12.0538(10)
13.1658(10)
99.6390(10)
90.2730(10)
93.4100(10)
1357.85(19)
2
9.275(3)
11.075(3)
28.066(8)
90.00
92.059(4)
90.00
2880.9(14)
4
1.645
12.395(3)
14.970(3)
15.151(3)
68.20(3)
87.43(3)
89.97(3)
2607.5(9)
2
1.510
1.013
1192
˚
b/A
˚
c/A
a (◦)
b (◦)
g (◦)
3
˚
V/A
Z
rc/g cm-3
1.389
0.743
576
m/mm-1
2.346
1416
F(000)
q range (deg)
Reflns collected
Indep. reflns
Refns obs.[I >2s(I)]
Data/restr./paras
GOF
1.72–26.00
7470 (Rint = 0.0284)
5238
4191
5238/319/0
1.115
0.0503/0.1072
0.0620/0.1090
0.890/-0.949
1.98–25.50
14240 (Rint = 0.0629)
5355
3965
5355/325/12
1.060
0.0646/0.1648
0.0895/0.1755
2.055/-1.395
1.63–25.02
13240 (Rint = 0.0243)
9076
6518
9076/605/61
1.086
0.0500/0.1260
0.0763/0.1387
0.862/-1.132
R1, wR2[I>2s(I)]
R1, wR2 (all data)
larg.peak/hole/e·A
-3
˚
Hz, 2H, p-cymene CH–(CH3)2), 3.83 (d, J = 3 Hz, 2H, Ru–CH2),
5.44, 5.47, 5.66, 5.92 (d, J = 6 Hz, 8H, p-cymene CH), 7.42 (s, 2H,
thiophene CH).
CCDC reference numbers 806364, 806363 and 806365 for 1, 3 and
5a, respectively.†
Acknowledgements
Synthesis of 6
This work was supported by the National Natural Science
Foundation of China (Nos. 20925104 and 21021062), the National
Basic Research Program of China (Nos. 2007CB925101 and
2010CB923303), the Natural Science Foundation of Jiangsu
Province (No.BK2010052) and the Ministry of Education of China
(No. 20090091110015).
The treatment of a solution of complex 4 (20 mg) in CH2Cl2
(20 mL) with silica in the presence of H2O at ambient temperature
leads to the ◦complex 6, a yellow solid, in a yield of 10.9 mg (53%).
1
m.p. = 175 C. H NMR (CDCl3): d 0.98 (d, J = 7 Hz, 3H, p-
cymene CH–CH3), 1.83 (d, J = 7 Hz, 3H, p-cymene CH–CH3),
2.23 (s, 3H, p-cymene CH3), 2.51 (s, 3H, O C–CH3), 2.68 (d, J = 3
Hz, 1H, Ru–CH2), 2.68 (sp, J = 7 Hz, 1H, p-cymene CH–(CH3)2),
3.86 (d, J = 3 Hz, 1H, Ru–CH2), 5.44, 5.47, 5.69, 5.94 (d, J = 6 Hz,
4H, p-cymene CH), 7.44 (d, J = 4 Hz, 1H, thiophene CH), 7.65
(d, J = 4 Hz, 1H, thiophene CH).11B NMR (CDCl3): d -1.3 (4B),
-3.4 (1B, JB–H = 130 Hz), -7.3 (3B), -10.0 (1B), -10.9 (1B, Ru–B).
EI–MS (70 eV): m/z 441 ([M–C8H6OS]+, 44%), 150 (C8H6OS+,
21%). IR (KBr): n (cm-1) 1635 (C O), 2580 (B–H). Anal. calcd
for C20H30S3B10RuO: C, 40.59; H, 5.11. Found: C, 40.41; H, 5.20%.
References
1 (a) S. X. Lu, G. X. Jin, S. Eibl, M. Herberhold and Y. Xin,
Organometallics, 2002, 21, 2533; (b) X. Y. Yu, G. X. Jin, N. H. Hu
and L. H. Weng, Organometallics, 2002, 21, 5540; (c) X. Y. Yu, S. X.
Lu, G. X. Jin and L. H. Weng, Inorg. Chim. Acta, 2004, 357, 361;
(d) J. Q. Wang, S. Y. Cai, G. X. Jin, L. H. Weng and M. Herberhold,
Chem.–Eur. J., 2005, 11, 7342.
2 (a) S. Y. Cai and G. X. Jin, Organometallics, 2005, 24, 4226; (b) S. Y.
Cai, J. Q. Wang and G. X. Jin, Organometallics, 2005, 24, 5280; (c) G.
X. Jin, J. Q. Wang, C. Zhang, L. H. Weng and M. Herberhold, Angew.
Chem., Int. Ed., 2005, 44, 259; (d) G. X. Jin, Coord. Chem. Rev., 2004,
248, 587; (e) X. Meng, F. Wang and G. X. Jin, Coord. Chem. Rev., 2010,
254, 1260.
Crystallographic analysis
The X-ray crystallographic data26 were collected on
a
Bruker SMART Apex II CCD diffractometer using graphite-
3 J. H. Won, D. H. Kim, B. Y. Kim, S. J. Kim, C. Lee, S. Cho, J. Ko and
S. O. Kang, Organometallics, 2002, 21, 1443.
˚
monochromated Mo-Ka (l = 0.71073 A) radiation. The intensities
4 (a) M. Herberhold, G. X. Jin, H. Yan, W. Milius and B. Wrackmeyer,
J. Organomet. Chem., 1999, 587, 252; (b) M. Herberhold, H. Yan, W.
Milius and B. Wrackmeyer, J. Organomet. Chem., 2000, 598, 142.
5 (a) X. Wang, S. Liu, L. H. Weng and G. X. Jin, Chem.–Eur. J., 2007,
13, 188; (b) S. Liu, G. L. Wang and G. X. Jin, Dalton Trans., 2008, 425;
(c) X. Q. Xiao and G. X. Jin, Dalton Trans., 2009, 9298.
6 (a) G. L. Wang, Y. J. Lin, O. Blacque, H. Berke and G. X. Jin, Inorg.
Chem., 2008, 47, 2940; (b) X. Q. Xiao, Y. J. Lin and G. X. Jin, Dalton
Trans., 2008, 2615.
were corrected for Lorentz polarization effects and empirical
absorption with the SADABS program. The structures were solved
by direct methods using the SHELXL-97 program. Crystal data,
data collection parameters and the results of the analyses of 1,
3 and 5a are listed in Table 2. Crystallographic data (excluding
structure factors) for the structural analysis of 1, 3 and 5a have
been deposited with the Cambridge Crystallographic Data Centre,
6996 | Dalton Trans., 2011, 40, 6992–6997
This journal is
The Royal Society of Chemistry 2011
©

View Article Online
7 (a) Y. G. Li, H. D. Ye, G. Guoyiqibayi, Q. B. Jiang, Y. Z. Li and H.
Yan, Sci. China Chem., 2010, 53, 2129; (b) H. D. Ye, G. Y. Ding, M.
S. Xie, Y. Z. Li and H. Yan, Dalton Trans., 2011, 40, 2306; (c) D. H.
Kim, J. Ko, K. Park, S. Cho and S. O. Kang, Organometallics, 1999, 18,
2738; (d) J. Y. Bae, Y. J. Lee, S. J. Kim, J. Ko, S. Cho and S. O. Kang,
Organometallics, 2000, 19, 1514.
8 M. Herberhold, H. Yan, W. Milius and B. Wrackmeyer, (a) Angew.
Chem., Int. Ed., 1999, 38, 3689; (b) Organometallics, 2000, 19, 4289;
(c) J. Organomet. Chem., 2000, 604, 170.
16 (a) L. B. Gao, J. Kan, Y. Fan, L. Y. Zhang, S. H. Liu and Z. N. Chen,
Inorg. Chem., 2007, 46, 5651; (b) C. C. Huang, Y. C. Lin, S. L. Huang,
Y. H. Liu and Y. Wang, Organometallics, 2003, 22, 1512; (c) C. Olivier,
B. S. Kim, D. Touchard and S. Rigaut, Organometallics, 2008, 27, 509.
17 (a) J. Maurer, B. Sarkar, B. Schwederski, W. Kaim, R. F. Winter and S.
Zalis, Organometallics, 2006, 25, 3701; (b) X. H. Wu, S. Jin, J. H. Liang,
Z. Y. Li, G. A. Yu and S. H. Liu, Organometallics, 2009, 28, 2450; (c) Q.
Y. Hu and G. C. Jia, Can. J. Chem., 2009, 87, 134.
18 V. I. Bregadze, Chem. Rev., 1992, 92, 209.
9 M. Herberhold, H. Yan, W. Milius and B. Wrackmeyer, (a) J.
Organomet. Chem., 2000, 604, 170; (b) Chem.–Eur. J., 2000, 6, 3026;
(c) Z. Anorg. Allg. Chem., 2000, 626, 1627; (d) Dalton Trans., 2001,
1782; (e) Chem.–Eur. J., 2002, 8, 388; (f) D. H. Wu, C. H. Wu, Y. Z. Li,
D. D. Guo, X. M. Wang and H. Yan, Dalton Trans., 2009, 285.
10 (a) B. H. Xu, D. H. Wu, Y. Z. Li and H. Yan, Organometallics, 2007,
26, 4344; (b) B. H. Xu, X. Q. Peng, Y. Z. Li and H. Yan, Chem.–Eur. J.,
2008, 14, 9347; (c) B. H. Xu, J. C. Tao, Y. Z. Li, S. H. Li and H. Yan,
Organometallics, 2008, 27, 334.
19 A. R. Siedle, Annu. Rep. NMR Spectrosc., 1988, 20, 205.
20 (a) B. Adolf, L. Akademie and W. Muenchen, Ber. Dtsch. Chem. Ges.,
1882, 15, 2705; (b) K. Don, K. Robert and N. Tim, J. Org. Chem., 1979,
17, 3076; (c) A. Annette, A. Giancarlo, P. Cristina, S. Andrew and T.
Thomas, Tetra. Lett., 1989, 11, 1315.
21 (a) N. S. Kozlov and G. P. Korotyshova, Vestsi Akademii Navuk BSSR,
Seryya Khimichnykh Navuk, 1975, 4, 106; (b) C. Raquel, C. Maria, L.
Mariano, R. Pilar and S. Sergio, J Am. Chem. Soc., 2003, 39, 11925.
22 M. A. Bennett, T. N. Huang, T. W. Matheson and A. K. Smith, Inorg.
Synth., 1982, 21, 74.
23 (a) L. Pu, Chem. Rev., 1998, 98, 2405; (b) X. W. Zou, S. W. Zhang, Y. X.
Cheng, Y. Liu, H. Huang and C. Y. Wang, J. Appl. Polym. Sci., 2007,
106, 821; (c) S. W. Zhang, Y. Liu, H. Huang, L. F. Zheng, L. L. Wu and
Y. X. Cheng, Synlett, 2008, 6, 853.
24 (a) T. X. Neenan and G. M. Whitesides, J. Org. Chem., 1988, 53, 2489;
(b) M. Lagasi and P. Moggi, J. Mol. Catal. A: Chem., 2002, 182–183,
61; (c) K. S. Schanze, E. E. Silverman and X. M. Zhao, J. Phys. Chem.
B, 2005, 109, 18451.
11 (a) Y. G. Li, Q. B. Jiang, X. L. Zhang, Y. Z. Li, H. Yan and V. I.
Bregadze, Inorg. Chem., 2010, 49, 3911; (b) Y. G. Li, Q. B. Jiang, Y. Z.
Li, H. Yan and V. I. Bregadze, Inorg. Chem., 2010, 49, 4.
12 N. E. Kolobova, O. S. Zhvanko, L. L. Ivanov, A. S. Batsanov and Y. T.
Struchkov, J. Organomet. Chem., 1986, 302, 235.
13 B. S. Newell, A. K. Rappe and M. P. Shores, Inorg. Chem., 2010, 49,
1595.
14 (a) J. M. Keller and K. S. Schanze, Organometallics, 2009, 28, 4210;
(b) S. Shanmugaraju, A. K. Bar, K. W. Chi and P. S. Mukherjee,
Organometallics, 2010, 29, 2971; (c) C. L. Ho, C. H. Chui, W. Y. Wong,
S. M. Aly, D. Fortin, P. D. Harvey, B. Yao, Z. Y Xie and L. X. Wang,
Macromol. Chem. Phys., 2009, 210, 1786.
25 (a) R. M. Whittal and L. Li, Anal. Chem., 1995, 67, 1950; (b) R. M.
Whittal, L. M. Russon, S. R. Weinberger and L. Li, Anal. Chem., 1997,
69, 2147.
15 E. Vergara, E. Cerrada, A. Casini, O. Zava, M. Laguna and P. J. Dyson,
Organometallics, 2010, 29, 2596.
26 Bruker, SMART, version 5.0, SAINT, version 6, SHELXTL, version
6.1, SADABS, version 2.03, Bruker AXS Inc., Madison, WI, 2000.
This journal is
The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 6992–6997 | 6997
©