Syntheses and structures of overcrowded silanedichalcogenols and their applications to the syntheses of silanedichalcogenolato complexes

Article abstract of DOI:10.1016/j.jorganchem.2008.11.001

Overcrowded silanedichalcogenols Tbt(Mes)Si(EH)(E′H), such as silanedithiol (E = E′ = S), hydroxysilanethiol (E = O, E′ = S) and hydroxysilaneselenol (E = O, E′ = Se), bearing an efficient combination of steric protection groups, Tbt and Mes (Tbt = 2,4,6-

Full text of DOI:10.1016/j.jorganchem.2008.11.001

Journal of Organometallic Chemistry 694 (2009) 353–365
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Journal of Organometallic Chemistry
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Syntheses and structures of overcrowded silanedichalcogenols
and their applications to the syntheses of silanedichalcogenolato complexes
1
*
Taro Tanabe, Yoshiyuki Mizuhata, Nobuhiro Takeda , Norihiro Tokitoh
Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan
a r t i c l e i n f o
a b s t r a c t
Overcrowded silanedichalcogenols Tbt(Mes)Si(EH)(E0H), such as silanedithiol (E = E0 = S), hydroxysila-
nethiol (E = O, E0 = S) and hydroxysilaneselenol (E = O, E0 = Se), bearing an efficient combination of steric
protection groups, Tbt and Mes (Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Mes = 2,4,6-trimethyl-
phenyl), were synthesized and isolated as air- and moisture-stable crystals, and their structures were
fully characterized by spectroscopic and elemental analyses together with X-ray crystallographic analy-
ses. The results of IR spectroscopy and the X-ray structural analyses suggested that these compounds
exist as monomers without any intra- and intermolecular interactions such as hydrogen bonds even in
Article history:
Received 2 October 2008
Received in revised form 31 October 2008
Accepted 4 November 2008
Available online 7 November 2008
Keywords:
Silanedithiol
the solid state and in solution. Novel four-membered-ring compounds, such as Tbt(Mes)Si(
and [Tbt(Mes)Si( -E)(
-E0)MLn] [E, E0 = O, S, Se; Pn = Sb, Bi; Bbt = 2,6-bis[bis(trimethylsilyl)methyl]-4-
[tris(trimethylsilyl)methyl]phenyl; MLn = Pd(PPh3)2, Pt(PPh3)2, Ru(
6-benzene)] were synthesized by uti-
l-S)2PnBbt
Hydroxysilanethiol
Hydroxysilaneselenol
Silanedithiolato complex
Platinum complex
Ruthenium complex
l
l
g
lizing the silanedichalcogenols as key building blocks. The molecular structures of these newly isolated
compounds were determined by NMR spectroscopic data together with X-ray crystallographic analyses.
Ó 2008 Elsevier B.V. All rights reserved.
1. Introduction
atom made it possible to isolate these highly reactive species.
These compounds are considered to be good precursors for the
The chemistry of organosilanethiols has been extensively stud-
ied and their wide utilities in organic synthesis have been reported
so far as H2S equivalents, homolytic reducing reagent for alkyl ha-
lides, polarity reversal catalysts (PRC), and so on [1,2]. Silanedithi-
ols are also interesting in their structures, properties, and utilities
as the building block for the synthesis of novel class of cyclic
organosilicon compounds. Silanedithiolato complexes, which are
expected as potential precursors for the controlled synthesis of
cyclic mixed-metal sulfido clusters [3], would be synthesized by
utilizing silanedithiols. However, silanedithiols are very rare and
their X-ray structural analyses have not been reported so far prob-
ably due to their high sensitivity toward H2O and extreme liability
to self-oligomerizations [4,5]. As for the main group element com-
pounds having two terminal SH groups on the central atom, there
are some examples of structurally characterized compounds, such
as TbtB(SH)2 (Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl) [6],
LAl(SH)2 (L = {N(Dip)C(Me)}2CH, Dip = 2,6-diisopropylphenyl) [7],
Dep(Dip)Ge(SH)2 (Dep = 2,6-diethylphenyl) [8]. It should be noted
that the introduction of (a) bulky substituent(s) on the central
syntheses of the corresponding dithiolates, which could be easily
converted to heterobimetallic sulfido clusters [6–8].
On the other hand, we have reported the synthesis and isolation
of a variety of highly reactive organosilicon compounds, such as
silicon–chalcogen double-bond compounds [9], silaaromatic com-
pounds [10], and silacyclopropabenzenes [11], by taking advantage
of an effective steric protection group, Tbt [12]. An overcrowded
cis-disilene 2, Tbt(Mes)Si@Si(Mes)Tbt, has been synthesized and
found to dissociate to the corresponding silylene 3, Tbt(Mes)Si:,
under mild conditions such as heating at 60 °C (Scheme 1) [13].
Very recently, we have reported the synthesis and properties of
silanedichalcogenolato titanium complexes, 6 and 7, by the dechal-
cogenation of the five-membered ring compounds, 4 and 5, which
were synthesized by the reactions of 3 with titanocenepentasulfide
and titanocenepentaselenide, respectively (Scheme 2) [14]. For the
development of our studies on the chemistry of silacyclic com-
pounds containing group 4 metal and chalcogen atoms, their zirco-
nium analogues, 8 or 9, have also been synthesized. They are
unprecedented and expected to be good precursors for the corre-
sponding silanedichalcogenols due to the high reactivity of zirco-
nium–chalcogen bonds. During the course of our studies, we
found the formation of stable silanedichalcogenols Tbt(Mes)Si(EH)
(E0H) 1a–c, silanedithiol (1a: E = E0 = S), hydroxysilanethiol (1b:
E = O, E0 = S), and hydroxysilaneselenol (1c: E = O, E0 = Se) [15]. In
addition, we have achieved the synthesis of silanedichalcogenolato
* Corresponding author. Tel.: +81774 38 3200; fax: +81 774 38 3209.
E-mail address: tokitoh@boc.kuicr.kyoto-u.ac.jp (N. Tokitoh).
1
Present address: Department of Chemistry and Chemical Biology, Graduate
School of Engineering, Gunma University, 1-5-1, Tenjin-cho, Kiryu, Gunma 376-8515,
Japan.
0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.11.001

354
T. Tanabe et al. / Journal of Organometallic Chemistry 694 (2009) 353–365
Scheme 1. Reactions of 2 with Cp2TiE5 (E@S,Se).
Scheme 2. Generation of silylene 3 from disilene 2.
Scheme 3. Syntheses of 8 and 9 and their hydration reactions.
complexes of group 10 transition metals by taking advantage of the
isolated silanedichalcogenols. Portions of this work were commu-
nicated as preliminary reports [16,17]. In this paper, we will report
the detailed synthesis, structures, and properties of the newly iso-
lated silanedichalcogenols and their applications to the synthesis
of novel four-membered-ring compounds consisting of one silicon
and two chalcogen atoms together with a heavier group 15 atom
[Sb,Bi] or a transition metal [Pd,Pt,Ru].
responding hydroxysilanethiol 1b (colorless crystals, 97%) (Scheme
4). Compounds 1b or 1c did not undergo any decomposition even
in the presence of O2 and H2O or during the separation process
with PTLC. Alternatively, silanedithiol 1a could be synthesized by
the reaction of tetrathiasilolane Tbt(Mes)SiS4 with 1.5 molar equiv.
of LiAlH4 at 0 °C in 83% isolated yield (Scheme 5). When this reac-
tion was carried out at room temperature, a mixture of 1a,
Tbt(Mes)Si(H)SH, and Tbt(Mes)SiH2 was obtained, suggesting the
over-reduction resulting from the reaction of hydrides with the
Si–S bond(s) together with the S–S bonds (see Scheme 3).
2. Results and discussions
2.2. Structures of silanedithiol 1a, hydroxysilanethiol 1b, and
hydroxysilaneselenol 1c
2.1. Synthesis of silanedichalcogenolato zirconium complexes and their
hydration reactions affording silanedichalcogenols 1a–c
The structures of silanedithiol 1a, hydroxysilanethiol 1b, and
hydroxysilaneselenol 1c were confirmed by the spectroscopic data
and elemental analyses, and finally determined by X-ray crystallo-
graphic analysis. The thermal ellipsoids of 1a–c are shown in Figs.
1–3 and the crystal data are summarized in Table 1. To the best of
our knowledge, these are the first examples of the X-ray structural
analyses of silanedithiol, hydroxysilanethiol, and hydroxysilanesel-
enol. The bond lengths of Si–S, Si–Se, and Si–O in 1a–c are typical
and the shortest intermolecular EꢁꢁꢁE distances (1a: Sꢁ ꢁ ꢁS 3.8594 Å,
The reaction of 2 with 2 molar equiv. of zirconocene pentasul-
fide at 60 °C afforded silanedithiolato zirconium complex [Tbt
(Mes)Si(
of 2 with 2 molar equiv. of zirconocene pentaselenide afforded the
selenium analogue, [Tbt(Mes)Si( -Se)2ZrCp2] (9). These are the
l-S)2ZrCp2] (8) in a moderate yield. Similarly, the reaction
l
first examples of silanedichalcogenolato zirconium complexes.
Although complexes 8 and 9 could not be isolated due to their high
sensitivity to the hydrolysis as compared with their titanium ana-
logues, their structures were suggested by the 29Si NMR chemical
shifts [dSi = ꢀ51.7 (8), dSi = ꢀ36.5 (9)], which are similar to those
of the four-membered-ring titanium analogues [dSi = ꢀ57.2 (6),
dSi = ꢀ52.7 (7)] and different from those of the five-membered-ring
ones [dSi = +46.5 (4), dSi = +32.0 (5)]. It is interesting that the four-
membered-ring compounds were obtained directly in contrast to
the titanium cases [14].
The reaction of 8 with excess of H2O gave silanedithiol 1a as col-
orless crystals, where the hydrolysis of the Zr–S bonds should oc-
cur selectively. On the other hand, the reaction of 9 with excess
of H2O afforded hydroxysilaneselenol 1c. Although silanediselenol,
Tbt(Mes)Si(SeH)2, was considered to be an intermediate in this
reaction, the intermediary silanediselenol could not be isolated
and observed due to its high sensitivity toward H2O. Isolated 1a
was found to be quite stable toward air and moisture and did
not decompose even in C6D6 solution in the presence of H2O for
1 day. When 1a was subjected to preparative thin-layer chroma-
tography (PTLC) on SiO2, it was converted quantitatively to the cor-
Scheme 4. Hydrolysis of 1a.
Scheme 5. Reactions of tetrathiasilorane with LiAlH4.

T. Tanabe et al. / Journal of Organometallic Chemistry 694 (2009) 353–365
355
Fig. 3. The thermal ellipsoid of 1c drawn at the 50% probability level. Hydrogen
atoms except for OH and SeH are omitted for clarity. Selected bond lengths (Å) and
angles (°). Si(1)–Se(1) 2.350(2), Si(1)–O(1) 1.635(6), Se(1)–Si(1)–O(1) 103.1(2).
Fig. 1. The thermal ellipsoid of 1a drawn at the 50% probability level. Hydrogen
atoms except for SH are omitted for clarity. Selected bond lengths (Å) and angles (°).
Si(1)–S(1) 2.1576(16), Si(1)–S(2) 2.1436(15), S(1)–Si(1)–S(2) 101.73(6).
Table 1
Crystal data and structure refinements for 1a–c.
1a
1b
1c
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
C36H72S2Si7
765.69
C36H72OSSi7
749.63
C36H72OSSi7
796.53
Triclinic
Triclinic
Triclinic
ꢀ
ꢀ
ꢀ
P1 (#2)
P1 (#2)
P1 (#2)
9.2535(4)
15.9925(5)
15.8055(7)
82.9726(15)
81.9726(15)
81.365(4)
2276.62(16)
2
9.3654(3)
13.0538(4)
21.1294(9)
72.5813(16)
77.9579(16)
71.303(3)
2316.41(14)
2
9.2373(6)
13.1271(4)
20.9732(14)
75.135(2)
80.846(2)
70.744(3)
2312.8(2)
2
b (Å)
c (Å)
a
(°)
b (°)
c
(°)
V (Å3)
Z
Dcalcd. (g cmꢀ3
)
1.117
0.324
1.075
0.276
1.144
1.018
l
(Mo K
a
) (mmꢀ1
)
Crystal size (mm)
Reflections
0.30 ꢂ 0.10 ꢂ 0.10 0.10 ꢂ 0.10 ꢂ 0.02 0.20 ꢂ 0.20 ꢂ 0.05
23256
19769
18622
collected
Independent
reflections
8315 (0.0772)
8097 (0.0885)
7955 (0.1003)
[R(int)
Parameters
R1 [I > 2 (I)]
wR2 (all data)
Goodness-of-fit
(GOF)
]
427
459
429
r
0.0563
0.1350
1.049
0.0855
0.1923
1.112
0.0962
0.2346
1.136
Fig. 2. The thermal ellipsoid of 1b drawn at the 50% probability level. Hydrogen
atoms except for OH and SH are omitted for clarity. Selected bond lengths (Å) and
angles (°). Si(1)–S(1) 2.192(2), Si(1)–O(1) 1.659(4), S(1)–Si(1)–O(1) 103.84(15).
Largest peak, hole
0.580, ꢀ0.471
0.806, ꢀ0.412
0.984, ꢀ0.682
(e Åꢀ3
)
1b: Sꢁ ꢁ ꢁO 3.319 Å, 1c: Seꢁ ꢁ ꢁO 3.500 Å) suggest the absence of the
intermolecular interactions such as hydrogen bonds between the
Eꢁ ꢁ ꢁH (E = O, S, Se) parts in the solid state (Fig. 4). The intramolec-
ular Eꢁ ꢁ ꢁE distances (1a: Sꢁ ꢁ ꢁS 3.3363 Å, 1b: Sꢁ ꢁ ꢁO 3.049 Å, 1c:
Seꢁ ꢁ ꢁO 3.152 Å) are slightly shorter than the sums of their van
der Waals radii (Sꢁ ꢁ ꢁS 3.60 Å, Sꢁ ꢁ ꢁO 3.32 Å, Seꢁ ꢁ ꢁO 3.42 Å) [18].
In IR spectra, it is well-known that the absorptions assignable to
the E–H (E = O, S, Se) vibrations with E–Hꢁ ꢁ ꢁE hydrogen bonding
should be broadened and shifted to the lower wavenumber region
[19]. The IR spectra of 1a, 1b, and 1c in the solid state (KBr or NaCl)
showed sharp peaks [1a: 2572 cmꢀ1 (S–H stretch), 1b: 2661 cmꢀ1
(S–H stretch), 3646 cmꢀ1 (O–H stretch), 1c: 2479 cmꢀ1 (Se–H
stretch), 3656 cmꢀ1 (O–H stretch)], suggesting the absence of the
intra- and intermolecular interactions such as hydrogen bonding(s)
between the E–H (E = O, S, Se) parts in the solid state. On the other
hand, their IR spectra in a CCl4 solution showed some signals in the
region of the normal E–H stretch vibrations. When the concentra-
tion of the CCl4 solution was changed, disappearance of these sig-
nals and appearance of new signals were not observed. In addition,
the sharp signals in the 1H NMR spectra assigned to the E–H pro-
tons (E = O, S, Se) of 1a–c [1a: dH = 1.18 (SH), 1b: dH = 0.87 (SH),
2.50 (OH), 1c: dH = ꢀ0.90 (SeH), 2.12 (OH)] were neither shifted
nor broadened on changing the concentrations. These results sug-
gested that the compounds 1a–c exist as a monomer without any
intermolecular interactions even in solution.

356
T. Tanabe et al. / Journal of Organometallic Chemistry 694 (2009) 353–365
Fig. 4. The crystal packing of silanedithiol 1a.
2.3. Synthesis of novel four-membered-ring compounds containing
heavier group 15 element: 1,3,2,4-dithiastibasiletane and 1,3,2,4-
dithiabismasiletane
Treatment of silanedithiol 1a with 2 molar equiv. of n-BuLi in
THF at 0 °C and the addition of excess methyl iodide resulted in
the quantitative formation of bis(methylthio)silane, Tbt(Mes)-
Si(SMe)2 (11) (Scheme 6 and Fig. 5). The exclusive formation of
11 can be explained in terms of the quantitative generation of
the corresponding dilithium silanedithiolate, Tbt(Mes)Si(SLi)2
(10a). The reaction of the 10a with 1 molar equiv. of Bbt-substi-
tuted dibromostibine or dibromobismuthine afforded the corre-
sponding 1,3-dithietane derivatives containing a silicon atom and
a heavier group 15 atom, 1,3,2,4-dithiastibasiletane (12) and
1,3,2,4-dithiabismasiletane (13), as pale yellow crystals in moder-
ate yields, respectively (Scheme 6).
The structures of 12 and 13 were revealed by X-ray structural
analysis. The structural parameters of 13 could not be discussed
in detail because of its inevitable disorder. Their four-membered-
ring cores were found to be almost planar. The extremely bulky
Tbt (on the silicon) and Bbt (on the antimony) groups of 12 were
attached to the four-membered-ring core in the trans position to
each other. The Si–S bond lengths of 12 were found to be slightly
Fig. 5. The thermal ellipsoid of 11 drawn at the 50% probability level. Hydrogen
atoms are omitted for clarity. Selected bond lengths (Å) and angles (°). Si(1)–S(1)
2.1546(18), Si(1)–S(2) 2.174(2), S(1)–C(1) 1.811(6), S(2)–C(2) 1.831(5), S(1)–Si(1)–
S(2) 103.00(8).
shorter than those of Tbt(Mes)Si(l-S)2Si(Mes)Tbt (14), and the
Sb–S bond lengths of 12 and BbtSb(
l-S)2SbBbt (15) were almost
Scheme 6. Generation of silanedithiolate 10a and its reactions with electrophiles.

T. Tanabe et al. / Journal of Organometallic Chemistry 694 (2009) 353–365
357
the Si–S bond cleavage [3]. However, chelating silanedithiolato
complexes, [R2Si( -S)2MLn], are less common due to the limitation
l
of an appropriate synthetic methodology. Typically, excess amount
of 1,3,5,2,4,6-trithiatrisilinane (SSiMe2)3 should be required as a
sulfur transfer reagent for the synthesis of silanedithiolato com-
plexes [3a]. The silanedithiol 1a was considered to be applicable
toward the development of a new synthetic strategy for silanedi-
thiolato transition metal complexes. The addition of cis-
[MCl2(PPh3)2] (M = Pd, Pt) to the THF solution of silanedithiolate
10a resulted in the almost quantitative formation of the corre-
sponding silanedithiolato complexes of palladium and platinum,
[Tbt(Mes)Si(l-S)2M(PPh3)2] (16: M = Pd, 17a: M = Pt), respectively,
as air- and moisture-stable yellow crystals (Scheme 7) [16]. Both of
the central four-membered rings in 16 and 17a consisting of Si,
two S, and Pd or Pt atoms have puckered structures (Figs. 7 and
8), although the corresponding PdS2Si ring of the silanedithiolato
palladium complex [Me2Si(l-S)2Pd(PEt3)2] reported by Tatsumi
et al. [3a] has an almost planar structure. This is probably due to
the steric repulsion between the extremely bulky Tbt group and
thiphenylphosphine moiety. In the 29Si NMR, the signals of the cen-
tral silicon atoms in the silanedithiolato complexes 16 (dSi = 15.3)
and 17a (dSi = 14.2) were observed in the region characteristic of
silanedithiolato late transition metal complexes [3] and lay in low-
er field than that of free ligand 1a (dSi = ꢀ1.8).
Fig. 6. The thermal ellipsoid of 12 drawn at the 50% probability level. Hydrogen
atoms are omitted for clarity. Selected bond lengths (Å) and angles (°). Si(1)–S(1)
2.1510(12), Si(1)–S(2) 2.1744(12), Sb(1)–S(1) 2.4515(9), Sb(1)–S(2) 2.4577(8), S(1)–
Si(1)–S(2) 98.97(5), S(1)–Sb(1)–S(2) 84.11(3), Si(1)–S(1)–Sb(1) 88.74(4), Si(1)–S(2)–
Sb(1) 88.05(3).
similar to those for the related compounds [15,20] (see Fig. 6 and
Table 2).
2.5. Synthesis of silaneoxylatochalcogenolato platinum complexes
The stable silanedithiol 1a was found to be a key species as a
building block for several types of silanedithiolato complexes. This
finding prompted us to investigate the synthetic utility of 1b and
1c for the synthesis of metal siloxides bridged by a sulfur or sele-
nium atom from the standpoints of structural elucidation for sila-
nedichalcogenolato complexes systematically. The reactions of 1b
or 1c with 2 molar equiv. of sodium hydride and the addition of
2.4. Synthesis of silanedithiolato complexes containing a group 10
transition metal
Silanethiolato or silanedithiolato complexes of late transition
metals have been known to be good precursors for mixed-metal
sulfido clusters via the ligand exchange reactions accompanying
Table 2
Crystal data and structure refinements for 11, 12, and 16.
11 ꢁ 0.5hexane
12 ꢁ 0.5benzene
16 ꢁ hexane ꢁ benzene
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
C38H76S2Si7 ꢁ 0.5(C6H14
)
C66H137S2SbSi14 ꢁ 0.5(C6H6)
C72H100P2PdS2Si7 ꢁ C6H14 ꢁ C6H6
836.82
1548.94
1558.89
Triclinic
Triclinic
Monoclinic
P21/c (#14)
12.43510(10)
19.5286(2)
36.7653(4)
90
91.1935(5)
90
8926.15(15)
4
ꢀ
ꢀ
P1 (#2)
P1 (#2)
9.3953(6)
12.5768(7)
24.2983(19)
93.186(3)
97.807(4)
113.381(7)
2592.0(3)
2
13.7523(2)
16.9131(3)
21.1525(4)
113.2919(12)
102.4982(7)
92.0075(7)
4371.81(13)
2
b (Å)
c (Å)
a
(°)
b (°)
c
(°)
V (Å3)
Z
Dcalcd. (g cmꢀ3
)
1.072
0.290
1.153
0.578
1.184
0.433
l
(Mo K
a
) (mmꢀ1
)
Crystal size (mm)
0.30 ꢂ 0.20 ꢂ 0.10
0.20 ꢂ 0.10 ꢂ 0.05
0.30 ꢂ 0.20 ꢂ 0.20
Reflections collected
Independent reflections [R(int)
Parameters
21491
89299
37331
]
8951 (0.1288)
474
15726 (0.0570)
867
15293 (0.0322)
984
R1 [I > 2
r
(I)]
0.0688
0.0419
0.0416
wR2 (all data)
0.1392
0.1022
0.1171
Goodness-of-fit (GOF)
1.032
0.497, ꢀ0.344
1.061
3.690, ꢀ0.837
1.048
1.245, ꢀ0.976
Largest peak, hole (e Åꢀ3
)
Scheme 7. Synthesis of silanedithiolato complexes containing a group 10 transition metal 16 and 17a.

358
T. Tanabe et al. / Journal of Organometallic Chemistry 694 (2009) 353–365
Fig. 9. The thermal ellipsoid of 17b drawn at the 50% probability level. Hydrogen
atoms are omitted for clarity. Selected bond lengths (Å) and angles (°). Si(1)–S(1)
2.1708(13), Si(1)–O(1) 1.636(3), Pt(1)–S(1) 2.3495(9), Pt(1)–O(1) 2.076(2), Pt(1)–
P(1) 2.2397(9), Pt(1)–P(2) 2.2758(10), S(1)–Si(1)–O(1) 97.07(10), Si(1)–O(1)–Pt(1)
100.02(12), Si(1)–S(1)–Pt(1) 78.34(4), S(1)–Pt(1)–O(1) 80.77(7), S(1)–Pt(1)–P(1)
87.48(3), P(1)–Pt(1)–P(2) 99.30(4), P(2)–Pt(1)–O(1) 93.27(7).
Fig. 7. The thermal ellipsoid of 16 drawn at the 50% probability level. Hydrogen
atoms are omitted for clarity. Selected bond lengths (Å) and angles (°). Si(1)–S(1)
2.1142(11), Si(1)–S(2) 2.1548(11), Pd(1)–S(1) 2.3242(8), Pd(1)–S(2) 2.3577(7),
S(1)–Si(1)–S(2) 95.48(4), S(1)–Pd(1)–S(2) 84.88(3).
Fig. 10. The thermal ellipsoid of 17c drawn at the 50% probability level. Hydrogen
atoms are omitted for clarity. Selected bond lengths (Å) and angles (°). Si(1)–Se(1)
2.3152(12), Si(1)–O(1) 1.635(3), Pt(1)–Se(1) 2.4565(5), Pt(1)–O(1) 2.067(3), Pt(1)–
P(1) 2.2324(12), Pt(1)–P(2) 2.2835(12), Se(1)–Si(1)–O(1) 95.82(11), Si(1)–O(1)–
Pt(1) 103.37(14), Si(1)–Se(1)–Pt(1) 75.32(3), Se(1)–Pt(1)–O(1) 81.47(8), Se(1)–
Pt(1)–P(1) 87.00(3), P(1)–Pt(1)–P(2) 99.71(4), P(2)–Pt(1)–O(1) 92.83(8).
Fig. 8. The thermal ellipsoid of 17a drawn at the 50% probability level. Hydrogen
atoms are omitted for clarity. Selected bond lengths (Å) and angles (°). Si(1)–S(1)
2.157(2), Si(1)–S(2) 2.115(2), Pt–S(1) 2.3667(15), Pt–S(2) 2.3333(17), S(1)–Si(1)–
S(2) 94.92(9), S(1)–Pt–S(2) 84.09(6).
[24.7 (1JPPt = 3206 Hz) and 6.2 (1JPPt = 3537 Hz) ppm]. It should be
cis-[PtCl2(PPh3)2] in THF afforded [Tbt(Mes)Si(l-O)(l-E)Pt(PPh3)2],
noted in both cases that the doublet signals at upper fields have
17b [E = S (89%)] and 17c [E = Se (95%)], respectively, as air- and
moisture-stable pale yellow crystals in high yields (Scheme 8)
[17]. When the reactions were performed by utilizing n-BuLi as a
base instead of sodium hydride, the same products were obtained
in similar yields. Their four-membered-ring cores have an almost
puckered geometry. Although the sum of the bond angles around
the platinum atoms of 17b and 17c are 360.82° and 361.01°,
respectively, the values of which are normal for the neutral cis-
platinum complexes two-valent and four-coordinated [21], their
central platinum atoms deviate from the planar geometry (Figs. 9
and 10 and Table 3). In the 31P{1H} NMR spectrum of 17b, two dis-
tinguishable doublet signals of triphenylphosphine ligands were
observed at 25.1 (1JPPt = 3209 Hz) and 6.9 (1JPPt = 3532 Hz) ppm.
They are slightly upfield shifted compared with those of 17c
1
larger JPPt coupling constants than those at lower fields have.
The doublet signals at 6.9 (17b) and 6.2 (17c) ppm are assigned
to the phosphorus atoms situated in the trans position to the oxy-
gen atom and the doublet signals at 25.1 (17b) and 24.7 (17c) ppm
are assigned to those in the trans position to the sulfur or selenium
atom. X-ray structural analyses revealed that Pt–P bond lengths
situated in the trans position to the oxygen atom [17b:
2.2327(9) Å; 17c: 2.2324(12) Å] are slightly shorter than those sit-
uated in the trans position to the sulfur [for 17b: 2.2758(10) Å] or
selenium atom [for 17c: 2.2835(12) Å], resulting from the trans
influence of the chalcogen atoms on the silicon atom. Taking the re-
sults of their 31P NMR into consideration, the trans influence of the
sulfur or the selenium atoms on the silicon atom is much larger
Scheme 8. Synthesis of silaneoxylatochalcogenolato platinum complexes 17b and 17c.

T. Tanabe et al. / Journal of Organometallic Chemistry 694 (2009) 353–365
359
Table 3
Crystal data and structure refinements for 17a, 17b, 17c, 18b, and 18c.
17a ꢁ hexane
17b ꢁ hexane
17c ꢁ 2benzene
18b
18c ꢁ benzene
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
C72H100P2PtS2Si7 ꢁ C6H14
C72H100OP2PtSSi7 ꢁ C6H14
C72H100OP2PtSeSi7 ꢁ 2(C6H6)
C42H76PORuSi7
926.79
C42H76ORuSeSi7 ꢁ C6H6
1569.47
1553.41
1670.36
1051.80
Triclinic
Triclinic
Triclinic
Monoclinic
C2/c (#15)
43.7641(6)
13.4000(3)
21.7659(9)
90
116.3546(17)
90
11437.7(6)
8
Monoclinic
C2/c (#15)
39.8562(16)
13.1996(7)
21.8447(13)
90
94.052(3)
90
11463.5(10)
8
ꢀ
ꢀ
ꢀ
P1 (#2)
P1 (#2)
P1 (#2)
13.7853(8)
16.8910(9)
21.0444(17)
113.276(7)
102.504(4)
92.842(3)
4344.4(5)
2
13.5758(2)
16.6860(4)
21.1691(4)
112.5927(8)
102.7127(9)
91.7477(9)
4283.43(15)
2
13.5365(9)
16.6705(12)
21.2730(19)
113.098(2)
104.790(2)
90.279(2)
4239.5(6)
2
b (Å)
c (Å)
a
(°)
b (°)
c
(°)
V (Å3)
Z
Dcalcd. (g cmꢀ3
)
1.200
1.833
1.204
1.836
1.309
2.263
1.076
0.483
1.219
1.086
l
(Mo K
a
) (mmꢀ1
)
Crystal size (mm)
0.20 ꢂ 0.10 ꢂ 0.10
0.20 ꢂ 0.10 ꢂ 0.10
0.30 ꢂ 0.20 ꢂ 0.20
0.20 ꢂ 0.10 ꢂ 0.10
0.15 ꢂ 0.10 ꢂ 0.10
Reflections collected
Independent reflections [R(int)
Parameters
36803
36449
35867
51664
46146
]
15211 (0.0689)
870
14966 (0.0311)
998
14860 (0.0422)
963
10066 (0.0728)
598
10024 (0.0773)
545
R1 [I > 2
r
(I)]
0.0511
0.0345
0.0445
0.0748
0.0666
wR2 (all data)
0.1272
0.0834
0.0803
0.1902
0.2018
Goodness-of-fit (GOF)
1.078
0.974, ꢀ0.918
1.065
1.462, ꢀ1.165
1.125
0.979, ꢀ0.521
1.164
3.763, ꢀ1.270
1.052
3.740, ꢀ1.082
Largest peak, hole (e Åꢀ3
)
Scheme 9. Synthesis of silanedichalcogenolato ruthenium complexes 18 and 19.
than that of the oxygen atom. On the other hand, the degree of
trans influence between sulfur and selenium are almost similar to
each other [22]. The 29Si NMR resonances in the central silicon
atoms of 17b (dSi = 5.3) and 17c (dSi = ꢀ3.3) lay in a lower field than
those of 1b (dSi = ꢀ5.3) and 1c (dSi = ꢀ9.5) and in a higher field than
that of silanedithiolato platinum complex 17a (dSi = 14.2).
viously [8a,23]. The UV–Vis spectra of 18a–c in hexane showed
characteristic absorptions of coordinatively unsaturated ruthe-
nium complexes [18a: 676 nm, 18b: 578 nm, 18 c: 610 nm] assign-
able to the HOMO–LUMO transition from the p
p orbitals of the
bridging chalcogens to the vacant d orbitals of the Ru atom [23].
These experimental results were supported by the TD-DFT calcula-
2.6. Synthesis of silanedichalcogenolato ruthenium complexes
Chalcogenolate ligands are known to possess a
r-donor orbital
along with lone pair orbitals that have the correct symmetry for
p-
interaction with a metal d orbital. Actually it has been demon-
strated that some of bulky thiolate ligands effectively stabilized
coordinatively unsaturated mononuclear complexes of late or mid-
dle transition metals [23]. The stable silanedichalcogenols 1a–c
were expected to be building blocks for coordinatively unsaturated
ruthenacycles. The addition of 0.5 molar equiv. of [RuCl2(g
6-ben-
zene)]2 to the THF solution of dilithium or disodium silanedichal-
cogenolates 10a–c, gave the corresponding silandichalcogenolato
ruthenium complexes 18a–c as deep green, deep violet, and deep
blue crystals, respectively, in moderate yields (Scheme 9). The X-
ray crystallographic analysis revealed their monomeric structures
and the molecular structures of 18b and 18c are shown in
Fig. 11. Their four-membered-ring cores have an almost planar
geometry and the dihedral angles between the four-membered-
ring cores and
planar geometry would enhance the
g
6-coordinated benzene rings are almost 90°. The
overlap between the p
p
p
orbitals of O, S, or Se atoms and the vacant d orbital of Ru atom
to ease the electron deficiency at Ru atom, as discussed for the re-
lated complexes in the previous reports [8a,23]. The Ru–E bonds of
18b [Ru–O = 1.991(4) Å, Ru–S = 2.3007(14) Å] and 18c [Ru–
O = 2.008(3) Å, Ru–Se = 2.3122(14) Å] are similar to the Ru–E bond
lengths of the electron-deficient ruthenium thiolates reported pre-
Fig. 11. The thermal ellipsoid of 18b drawn at the 50% probability level. Hydrogen
atoms are omitted for clarity. Selected bond lengths (Å) and angles (°). Si(1)–O(1)
1.628(4), Si(1)–S(1) 2.149(2), Ru(1)–S(1) 2.3007(14), Ru(1)–O(1) 1.991(4), S(1)–
Si(1)–O(1) 95.79(16), Si(1)–O(1)–Ru(1) 102.8(2), Si(1)–S(1)–Ru(1) 79.18(6), S(1)–
Ru(1)–O(1) 81.95(11).

360
T. Tanabe et al. / Journal of Organometallic Chemistry 694 (2009) 353–365
Company) [24]. C6D6 used as a solvent was dried over Na, then K
mirror. The 1H NMR (300 or 400 MHz) spectra were measured in
CDCl3 or C6D6 with a JEOL AL-400 or AL-300 spectrometer using
residual CHCl3 (7.25 ppm) or C6D5 H (7.15 ppm) as an internal
standard. 13C NMR (75 MHz) spectra were recorded on a JEOL
JNM AL-300 spectrometer. 13C NMR chemical shifts were reported
in ppm downfield from tetramethylsilane and referenced to the
carbon signal of CDCl3 (77.0 ppm) or C6D6 (128.0 ppm). Multiplic-
ity of signals in 13C NMR spectra was determined by DEPT tech-
nique. The 29Si NMR (59 MHz), 31P NMR (120 MHz), 77Se NMR
(95 MHz), and 195Pt NMR (64 MHz) spectra were recorded on a
JEOL JNM AL-300 spectrometer. IR spectra were recorded on a JAS-
CO FT/IR-5300 spectrometer. High- and low-resolution mass spec-
tral data were obtained on a JEOL JMS-700 spectrometer. Elemental
analyses were carried out at the Microanalytical Laboratory of the
Institute for Chemical Research, Kyoto University. All melting
points were measured on a Yanaco micro melting points apparatus
and uncorrected. Wet column chromatography (WCC) and pre-
parative thin-layer chromatography (PTLC) were performed using
Wakogel C-200 and Merk Kieselgel 60 PF254, respectively. GPLC
(gel permeation liquid chromatography) was performed on LC-
908, LC-918 (Japan Analytical Industry Co., Ltd. Systems) equipped
with JAIGEL 1H and 2H columns (eluent: toluene). Tbt(Mes)SiS4
[25], Tbt(Mes)Si@Si(Mes)Tbt [25], [Cp2ZrE5] (E = S, Se) [26],
Fig. 12. The thermal ellipsoid of 18c drawn at the 50% probability level. Hydrogen
atoms are omitted for clarity. Selected bond lengths (Å) and angles (°). Si(1)–O(1)
1.629(5), Si(1)–Se(1) 2.312(2), Ru(1)–Se(1) 2.4206(9), Ru(1)–O(1) 2.016(4), Se(1)–
Si(1)–O(1) 95.23(18), Si(1)–O(1)–Ru(1) 105.6(2), Si(1)–Se(1)–Ru(1) 75.96(5), Se(1)–
Ru(1)–O(1) 82.71(13).
BbtPnBr2 (Pn = Sb, Bi) [27], and [RuCl2(g
6-benzene)]2 [28] were
prepared according to the reported methods.
tions [TD-B3LYP/6-31G(d) (LANL2DZ on Ru)//B3LYP/6-31G(d)
(LANL2DZ on Ru); Tbt and Mes were replaced by 2,6-dimethyl-
phenyl]. Despite the coordinative unsaturation of the Ru atom,
these complexes are quite stable in the air and even in solution
due to the effective combination of steric protection by Tbt and
Mes groups. The reactions of 18a–c with excess of PMe3 in THF re-
4.2. Synthesis of Tbt(Mes)Si(SH)2 (1a); hydrolysis of the
[Tbt(Mes)Si(l-S)2ZrCp2]
In a 5/ Pyrex glass tube was placed a THF solution (0.5 mL) of a
mixture of disilene Tbt(Mes)Si@Si(Mes)Tbt (59.8 mg, 0.0424
mmol) and [Cp2ZrS5] (36.2 mg, 0.0961 mmol). After three freeze-
pump-thaw cycles, the tube was evacuated and sealed. The solu-
tion was heated at 60 °C for 20 h, during which time the original
orange suspension turned into a pale orange solution. The tube
was opened and the solvent was removed under reduced pressure
in a glovebox filled with argon. Benzene (5 ml) was added to the
residue, and the mixture was filtered through CeliteÒ. After the re-
moval of the solvent, C6D6 (0.5 ml) was added to the mixture. The
measurement of 1H and 29Si NMR spectra indicated the formation
sulted in the replacement of the
PMe3 ligands leading to the quantitative formation of [Tbt(Mes)-
Si( -E)(
-E0)Ru(PMe3)3] (19a–c). The reactions of 18a–c with
g
6-benzene ligand with three
l
l
1 molar equiv. of PMe3 afforded the mixture of 18 (ca. 70%) and
19 (ca. 30%), in all cases. The bulky substituents on the silicon
atoms may prevent the formation of the coordinatively saturated
addition products, such as [Tbt(Mes)Si(
zene)(PMe3)] or [Tbt(Mes)Si(l-E)(l
l-E)(
l g
-E0)Ru( 6-ben-
-E0)Ru(PMe3)4] (see Fig. 12).
3. Conclusion
of [Tbt(Mes)Si(
l
-S)2ZrCp2] (dSi = ꢀ51.7, ꢃ40%) and 1,2,3,4,5-tetra-
thiasilolane, Tbt(Mes)SiS4, (dSi = 32.0, ꢃ30%), respectively, the
yields of which were judged by the ratio of the integrated intensity
of the 1H NMR. The THF solution of the reaction mixture containing
In summary, overcrowded silanedichalcogenols Tbt(Mes)Si(EH)
(E0H) (1a: E = E0 = S, 1b: E = O, E0 = S, 1c: E = O, E0 = Se), bearing an
efficient combination of steric protection groups, Tbt and Mes,
were synthesized and isolated as air- and moisture-stable crystals.
These new compounds were fully characterized by the spectro-
scopic data, elemental analyses, and X-ray structural analyses.
Silanedichalcogenols 1 were found to exist as a monomer without
any intermolecular contact such as hydrogen bonds both in the
solid state. Novel four-membered silacyclic compounds, [Tbt(Mes)
[Tbt(Mes)Si(l-S)2ZrCp2] and Tbt(Mes)SiS4 was opened in the air
and the solvent was removed. Benzene (5 ml) was added to the
residue, and the mixture was filtrated through CeliteÒ. After con-
centration under reduced pressure, the residue was separated by
GPLC (toluene) and silica gel chromatography (hexane) to afford
pure silanedithiol 1a (30.2 mg, 0.0394 mmol, 41%) as a colorless
solid together with 1,2,3,4,5-tetrathiasilolane, Tbt(Mes)SiS4
(25.6 mg, 0.0250 mmol, 26%), as a colorless solid. Colorless crystals
of 1a suitable for X-ray structural analysis were grown from hex-
ane. 1a: colorless crystals, m.p. 177–178 °C; 1H NMR (300 MHz,
CDCl3) d ꢀ0.02 (s, 18H), 0.00 (s, 18H), 0.04 (s, 18H), 1.18 (s, 2H,
SH), 1.31 (s, 1H), 2.22 (s, 3H), 2.49 (s, 1H), 2.57 (s, 6H), 2.63 (s,
1H), 6.24 (s, 1H), 6.38 (s, 1H), 6.76 (s, 2H); 13C{1H} NMR
(75 MHz, CDCl3) d 0.9 (CH3), 1.6 (CH3), 1.9 (CH3), 20.9 (CH3), 26.4
(CH3), 28.0 (CH), 28.3 (CH), 30.6 (CH), 123.3 (CH), 126.3 (C),
128.5 (CH), 130.5 (CH), 134.9 (C), 139.7 (C), 142.8 (C), 145.5 (C),
151.9 (C), 152.2 (C); 29Si NMR (59 MHz, CDCl3) d ꢀ1.8, 1.9, 2.9,
Si(
l-S)2PnBbt] (12: Pn = Sb, 13: Pn = Bi) or [Tbt(Mes)Si(l-E)(l
-E0)
MLn] [16: MLn = Pd(PPh3)2, 17: MLn = Pt(PPh3)2, 18: MLn = Ru(g6
-
benzene), 19: MLn = Ru(PMe3)3], were synthesized by utilizing
1a–c as key building blocks. Further investigations on their reactiv-
ities are currently under way.
4. Experimental
4.1. General experimental details
All experiments were performed under anhydrous conditions
under an argon atmosphere unless otherwise noted. All solvents
used in the reactions were purified prior to use by the standard
methods and/or by the Ultimate Solvent System (Glass Contour
3.0; IR (KBr) 2572 [m
(S–H)]; LRMS (FAB+) m/z: calcd. for C36H72S2Si7
([M]+) 764, found 764; HRMS (FAB+) m/z: calcd. for C36H72S2Si7
([M]+) 764.3460, found 764.3472. Anal. Calc. for C36H72S2Si7: C,
56.47; H, 9.48; S, 8.38. Found: C, 56.51; H, 9.57; S, 8.81%.

T. Tanabe et al. / Journal of Organometallic Chemistry 694 (2009) 353–365
361
4.3. Synthesis of Tbt(Mes)Si(SH)2 (1a); reaction of Tbt(Mes)SiS4 with
LiAlH4
ꢀ96.4; IR (KBr) 3511 [
m
(O–H)], 2479 [
m
(Se–H)]; LRMS (FAB+) m/z:
calcd. for C36H72O80SeSi7 ([M]+) 796, found 796; HRMS (FAB+) m/
z: calcd. for C36H72O80SeSi7 ([M]+) 796.3133, found 796.3101. Anal.
Calc. for C36H72OSeSi7: C, 54.28; H, 9.11. Found: C, 54.52; H, 9.05%.
To a solution of Tbt(Mes)SiS4 (165 mg, 0.238 mmol) in THF
(15 mL) was added LiAlH4 (13.5 mg, 0.356 mmol) at 0 °C. After
the mixture was stirred at 0 °C for 1 h, ethyl acetate (5 mL) was
added. After the removal of the solvent, hexane (3 mL) was added
to the residue. The suspension was filtrated through CeliteÒ, and
the solvent was removed under reduced pressure. The residue
was separated with silica gel chromatography (hexane) to afford
Tbt(Mes)Si(SH)2 1a (150 mg, 0.196 mmol, 83%).
4.6. Synthesis of Tbt(Mes)Si(SMe)2 (11)
To a solution of 1a (40.0 mg, 0.0522 mmol) in THF (3 mL) was
added n-BuLi (1.64 N hexane solution, 0.0800 mL, 0.131 mmol) at
0 °C. After the mixture was stirred at 0 °C for 30 min, iodomethane
(0.976 mL, 15.7 mmol) was added. After the removal of the solvent,
hexane (10 mL) was added to the residue. The mixture was fil-
trated through CeliteÒ, and the solvent was removed under re-
duced pressure. The residue was separated with PTLC (hexane) to
afford 11 (40.2 mg, 0.0506 mmol, 97%) as a colorless solid. Color-
less crystals suitable for X-ray structural analysis were grown from
hexane at ꢀ20 °C. 11: colorless crystals, m.p. 138–140 °C; 1H NMR
(300 MHz, CDCl3) d 0.04 (s, 36H), 0.06 (s, 18H), 1.29 (s, 1H), 1.87 (s,
6H, SMe), 2.21 (s, 3H), 2.49 (s, 1H), 2.59 (s, 6H), 2.63 (s, 1H), 6.23 (s,
1H), 6.38 (s, 1H), 6.75 (s, 2H); 13C{1H} NMR (75 MHz, CDCl3) d 0.86
(CH3), 1.01 (CH3), 1.68 (CH3), 1.96 (CH3), 13.02 (CH3, SMe), 20.85
(CH3), 24.63 (CH3), 28.54 (CH), 28.97 (CH), 29.70 (CH), 122.87 (C),
122.96 (C), 126.98 (C), 128.10 (C), 130.17 (CH), 130.60 (C),
139.22 (CH), 144.31 (CH), 144.77 (C), 150.62 (C); 29Si NMR
(59 MHz, CDCl3) d 1.84, 3.03, 8.21; LRMS (FAB+) m/z: calcd. for
C38H76Si7S2 ([M]+) 792, found 792; HRMS (FAB+) m/z: calcd. for
C38H76Si7S2 ([M]+) 792.3773, found: 792.3790. Anal. Calc. for
C38H76S2Si7: C, 57.50; H, 9.65; S, 8.08. Found: C, 57.75; H, 9.62; S,
8.12%.
4.4. Synthesis of Tbt(Mes)Si(OH)SH (1b)
Treatment of Tbt(Mes)Si(SH)2 1a (51.2 mg, 0.0668 mmol) on
PTLC (SiO2/hexane) afforded Tbt(Mes)Si(OH)SH 1b (46.6 mg,
0.0622 mmol, 93%). Colorless crystals suitable for X-ray structural
analysis of 1b were grown from hexane at ꢀ20 °C. 1b: colorless
crystals, m.p. 169–171 °C; 1H NMR (300 MHz, CDCl3) d ꢀ0.14 (s,
9H), 0.09 (s, 9H), 0.04 (s, 18H), 0.06 (s, 18H), 0.87 (s, 1H, SH),
1.31 (s, 1H), 2.22 (s, 3H), 2.48 (s, 6H), 2.50 (s, 1H, OH), 2.53 (s,
1H), 2.68 (s, 1H), 6.24 (s, 1H), 6.38 (s, 2H), 6.75 (s, 1H); 13C{1H}
NMR (75 MHz, CDCl3) d 0.9 (CH3), 1.1 (CH3), 1.2 (CH3), 1.7 (CH3),
21.2 (CH3), 25.2 (CH3), 27.8 (CH), 28.0 (CH), 30.8 (CH) 123.3 (CH),
127.5 (C), 128.4 (CH), 130.1 (CH), 135.4 (C), 139.9 (C), 143.1 (C),
145.3 (C), 151.4 (C), 151.6 (C); 29Si NMR (59 MHz, CDCl3) d –5.3,
2.1, 2.2, 2.7, 2.9, 3.2; IR (KBr) 2561 [m(S–H)], 3648 [m(O–H)]; LRMS
(FAB+) m/z: calcd. for C36H72OSSi7 ([M]+) 748, found 748; HRMS
(FAB+) m/z: calcd. for C36H72OSSi7 ([M]+) 748.3689, found
748.3690. Anal. Calc. for C36H72OSSi7: C, 57.68; H, 9.68; S, 4.28.
Found: C, 57.84; H, 9.74; S, 4.09%.
4.7. Synthesis of Tbt(Mes)Si(l-S)2SbBbt (12)
4.5. Synthesis of Tbt(Mes)Si(OH)SeH (1c); hydrolysis of the
[Tbt(Mes)Si(l-Se)2ZrCp2]
To a solution of 1a (83.5 mg, 0.109 mmol) in THF (5 mL) was
added n-BuLi (1.64 N hexane solution, 0.166 mL, 0.273 mmol) at
0 °C. After the mixture was stirred at 0 °C for 30 min, a THF
(10 mL) solution of BbtSbBr2 (148 mg, 0.164 mmol) was added.
After the removal of the solvent, hexane (10 mL) was added to
the residue. The mixture was filtrated through CeliteÒ, and the sol-
vent was removed under reduced pressure. The residue was sepa-
rated with GPLC (toluene) and WCC (hexane) to afford 12 (52.3 mg,
0.0346 mmol, 32%) as a pale yellow solid. Pale yellow crystals suit-
able for X-ray structural analysis were grown from hexane at
ꢀ20 °C. 12: pale yellow crystals, m.p. 147 °C (dec.); 1H NMR
(300 MHz, C6D6) d 0.20 (s, 18H), 0.24 (s, 36H), 0.31 (s, 27H), 0.33
(s, 36H), 1.53 (s, 1H), 2.08 (s, 3H), 2.41 (s, 2H), 2.78 (s, 6H), 3.29
(s, 1H), 3.41 (s, 1H), 6.50 (s, 1H), 6.68 (s, 2H), 6.70 (s, 1H), 6.96
(s, 2H); 13C{1H} NMR (75 MHz, C6D6) d 1.21 (CH3), 1.59 (CH3),
2.12 (CH3), 5.64 (CH3), 20.79 (CH3), 22.76 (CH3), 25.90 (CHꢂ2),
29.10 (CH), 31.88 (CH), 32.57 (CH), 122.06 (CH), 128.26 (CH),
128.29 (CH), 129.13 (C), 130.73 (CH), 131.32 (C), 139.31 (C),
140.95 (C), 141.87 (C), 143.69 (C), 145.42 (C), 147.35 (C), 150.49
(C), 152.59 (C); 29Si NMR (59 MHz, C6D6) d 1.16, 2.08, 2.37, 2.97,
3.18, 31.3; LRMS (FAB+) m/z: calcd. for C66H137S2123SbSi14 1510,
found 1510; HRMS (FAB+) m/z: calcd. for C66H137S2123SbSi14
([M]+) 1508.5973, found: 1508.5959. Anal. Calc. for
C66H137S2SbSi14: C, 52.50; H, 9.15; S, 4.25. Found: C, 52.86; H,
9.28; S, 4.09%.
In a 5/ Pyrex glass tube was placed a THF solution (0.5 mL) of a
mixture of Tbt(Mes)Si@Si(Mes)Tbt (30.6 mg, 0.0215 mmol) and
[Cp2ZrSe5] (28.4 mg, 0.0461 mmol). After three freeze-pump-thaw
cycles, the tube was evacuated and sealed. The solution was heated
at 60 °C for 20 h, during which time the original orange suspension
turned into a deep red solution. The tube was opened and the sol-
vent was removed under reduced pressure in a glovebox filled with
argon. Benzene (5 ml) was added to the residue, and the mixture
was filtered through CeliteÒ. After concentration under reduced
pressure, C6D6 (0.5 ml) was added to the mixture and the measure-
ment of 1H and 29Si NMR spectra indicated the formation of
[Tbt(Mes)Si(
l
-Se)2ZrCp2] (dSi = ꢀ36.5, ꢃ60%), the yield of which
was judged by the ratio of the integrated intensity of the 1H
NMR. The THF solution of the reaction mixture containing
[Tbt(Mes)Si(l-Se)2ZrCp2] was opened in the air and the solvent
was removed. After the residue was dissolved in benzene and fil-
trated through CeliteÒ, the solvent was removed again under re-
duced pressure. The residue was separated by GPLC (toluene) to
afford pure hydroxysilaneselenol 1c (21.2 mg, 0.0285 mmol, 62%)
as an orange solid. Pale orange crystals suitable for X-ray structural
analysis of 1c were grown from hexane at ꢀ20 °C. 1c: pale orange
crystals, m.p. 76 °C (dec.); 1H NMR (300 MHz, C6D6) d 0.90 (s, 1H,
1JSeH = 48.4 Hz, SeH), 0.09 (s, 9H), 0.12 (s, 9H), 0.17 (s, 18H), 0.27
(s, 9H), 0.28 (s, 9H), 1.47 (s, 1H), 2.07 (s, 3H), 2.12 (s, 1H, OH),
2.51 (s, 6H), 2.77 (s, 1H), 2.86 (s, 1H), 6.49 (s, 1H), 6.62 (s, 1H),
6.68 (s, 2H); 13C{1H} NMR (75 MHz, C6D6) d 1.00 (CH3), 1.13
(CH3), 1.40 (CH3), 1.86 (CH3), 2.16 (CH3), 20.92 (CH3), 25.23
(CH3), 28.10 (CH), 28.39 (CH), 30.94 (CH), 123.46 (CH), 128.11
(C), 128.53 (CH),130.23 (CH), 136.71 (C), 139.74 (C), 142.72 (C),
145.21 (C), 151.38 (C), 151.65(C); 29Si NMR (59 MHz, C6D6) d
ꢀ9.53, 2.02,2.08, 2.76, 3.16, 3.28; 77Se NMR (95 MHz, C6D6) d
4.8. Synthesis of Tbt(Mes)Si(l-S)2BiBbt (13)
To a solution of 1a (98.7 mg, 0.129 mmol) in THF (5 mL) was
added n-BuLi (1.64 N hexane solution, 0.157 mL, 0.257 mmol) at
0 °C. After the mixture was stirred at 0 °C for 30 min, a THF
(10 mL) solution of BbtBiBr2 (128 mg, 0.129 mmol) was added.
After the removal of the solvent, hexane (10 mL) was added to
the residue. The mixture was filtrated through CeliteÒ, and the sol-

362
T. Tanabe et al. / Journal of Organometallic Chemistry 694 (2009) 353–365
vent was removed under reduced pressure. The residue was sepa-
rated with GPLC (toluene) and WCC (hexane) to afford 13 (117 mg,
0.0735 mmol, 52%) as an orange solid. Orange crystals of 13 suit-
able for X-ray structural analysis were grown from hexane at
ꢀ20 °C. 13: orange crystals, m.p. 122 °C (dec.); 1H NMR
(300 MHz, C6D6) d 0.21 (s, 18H), 0.22 (s, 36H), 0.32 (s, 27H), 0.33
(s, 36H), 1.53 (s, 1H), 2.09 (s, 3H), 2.23 (s, 2H), 2.93 (s, 6H), 3.46
(s, 2H), 6.59 (s, 1H), 6.68 (s, 2H), 6.70 (s, 1H), 7.40 (s, 2H);
13C{1H} NMR (75 MHz, C6D6, 323 K) d 1.22 (CH3), 1.44 (CH3), 2.30
(CH3), 5.63 (CH3), 20.81 (CH3), 22.95 (CH), 26.35 (CH3), 28.94
(CH), 31.17 (CH), 34.71 (CHꢂ2), 127.79 (C), 128.10 (CH), 128.53
(CH), 130.96 (CH), 130.98 (CH), 133.14 (C), 138.98 (C), 141.96 (C),
143.79 (C), 144.91 (C), 146.36 (C), 151.99 (C), 152.17 (C), 152.23
(C); 29Si NMR (59 MHz, C6D6, 323 K) d 1.14, 1.75, 1.98, 2.93, 3.20,
7.06; LRMS (FAB+) m/z: calcd. for C66H137BiS2Si14 1595, found
1595; HRMS (FAB+) m/z: calcd. for C66H137BiS2Si14 ([M]+)
1595.6814, found 1595.6798. Anal. Calc. for C66H137BiS2Si14: C,
49.63; H, 8.65; S, 4.02. Found: C, 49.89; H, 8.57; S, 3.74%.
C6D6) d 1.2 (CH3), 2.1 (CH3), 2.5 (CH3), 21.1 (CH3), 25.3 (CH), 25.6
(CH), 26.9 (CH3), 30.5 (CH), 127.8 (CH), 128.3 (CH), 128.5 (CH),
4
3
128.6 (d, JCP = 1.2 Hz, CH), 131.41 (d, JCP = 1.9 Hz. CH), 131.42
1
3
(dd, JCP = 54.9 Hz, JCP = 6.8 Hz, C), 135.3 [AA0X pattern, 1/
2(2JCP + 4JCP) = 5.5 Hz, CH], 136.6 (C), 137.9 (C), 141.9 (C), 143.1
(C), 143.3 (C), 151.3 (C), 151.6 (C); 29Si NMR (59 MHz, C6D6) d
1.6, 2.5, 14.1; 31P NMR (120 MHz, C6D6) d 21.2 (s, with platinum
1
satellites, JPPt = 3047 Hz); 195Pt NMR (64 MHz, C6D6, Na2PtCl4) d
ꢀ4527.7 (t, JPPt = 3047 Hz); LRMS (FAB+) m/z: calcd. for
1
C72H100P2195PtS2Si7 ([M]+) 1481, found 1481; HRMS (FAB+) m/z:
calcd. for C72H100P2195PtS2Si7 ([M]+) 1481.4774, found 1481.4771.
Anal. Calc. for C72H100P2PtS2Si7: C, 58.30; H, 6.80; S, 4.32. Found:
C, 58.39; H, 6.89; S, 4.31%.
4.11. Synthesis of [Tbt(Mes)Si(l-O)(l-S)Pt(PPh3)2] (17b)
To a solution of 1b (60.1 mg, 0.0802 mmol) in THF (3 mL) was
added NaH (4.23 mg, 0.176 mmol) at 0 °C. After the mixture was
stirred at 0 °C for 30 min,
a THF solution (15 mL) of cis-
4.9. Synthesis of [Tbt(Mes)Si(
l
-S)2Pd(PPh3)2] (16)
[PtCl2(PPh3)2] (63.4 mg, 0.0802 mmol) was added, and the mixture
was stirred for 30 min at 0 °C and then for 1.5 h while being
warmed up to room temperature. After the removal of the solvent,
hexane (5 mL) was added to the residue. The mixture was filtrated
through CeliteÒ, and the solvent was removed under reduced pres-
sure. The residue was recrystallized from hexane at ꢀ20 °C to give
pure 17b (105 mg, 0.0714 mmol, 89%) as pale yellow crystals. 17b:
pale yellow crystals, m.p. 185 °C (dec.); 1H NMR (300 MHz, C6D6) d
0.21 (s, 18H), 0.23 (s, 36H), 1.50 (s, 1H), 2.40 (s, 3H), 2.61 (s, br, 3H),
2.84 (s, br, 3H), 6.52 (s, 1H), 6.65 (s, 1H), 6.76 (sꢂ2, br, 2H), 6.81–
6.87 (m, 6H), 6.90–6.97 (m, 12H), 7.40–7.46 (m, 6H), 7.59–7.63 (m,
6H), o-benzyl protons of the Tbt group could not be observed be-
cause of the overlap with those of the Mes group; 13C{1H} NMR
To a solution of 1a (69.9 mg, 0.0913 mmol) in THF (5 mL) was
added n-BuLi (1.64 N hexane solution, 0.156 mL, 0.256 mmol) at
0 °C, during which time the original colorless solution turned pale
yellow. After the mixture was stirred at 0 °C for 30 min, a THF solu-
tion (15 mL) of cis-[PdCl2(PPh3)2] (96.1 mg, 0.137 mmol) was
added. The pale yellow solution turned deep brown. After the re-
moval of the solvent, benzene (3 mL) was added to the residue.
The mixture was filtrated through CeliteÒ, and the solvent was re-
moved under reduced pressure. The residue was separated with
GPLC (toluene) to afford 16 (114 mg, 0.0819 mmol, 90%) as an or-
ange solid. Orange crystals suitable for X-ray structural analysis
were grown from hexane and benzene. 16: orange crystals, m.p.
214 °C (dec.); 1H NMR (300 MHz, C6D6) d 0.22 (s, 18H), 0.29 (s,
18H), 0.34 (s, 18H), 1.50 (s, 1H), 2.29 (s, 3H), 2.72 (s, 1H), 2.91 (s,
1H), 2.94 (s, 6H), 6.50 (s, 1H), 6.62 (s, 1H), 6.83 (s, 2H), 6.83–6.93
(m, 18H, PPh3), 7.45–7.56 (m, 12H, PPh3); 13C{1H} NMR (75 MHz,
C6D6) d 1.2 (CH3), 2.2 (CH3), 2.5 (CH3), 21.1 (CH3), 25.5 (CH), 27.0
(CH3), 30.4 (CH), 123.5 (CH), 128.0 [AA0X pattern, 1/
2(3JCP + 5JCP) = 4.9 Hz, CH], 128.6 (CH), 123.0 (CH), 130.1 (CH),
132.0 [AA0X pattern, 1/2(1JCP + 3JCP) = 21.6 Hz, C], 135.2 [AA0X pat-
tern, 1/2(2JCP + 4JCP) = 5.9 Hz, CH], 136.2 (C), 136.6 (C), 141.9 (C),
143.0 (C), 143.4 (C), 150.8 (C), 151.5 (C); 29Si NMR (59 MHz,
C6D6) d 1.8, 2.6, 15.2; 31P NMR (120 MHz, C6D6) d 30.6; LRMS
(FAB+) m/z: calcd. for C72H100P2108PdS2Si7 ([M]+) 1394, found
1394; HRMS (FAB+) m/z: calcd. for C72H101P2108PdS2Si7 ([M+H]+)
1395.4244, found 1395.4236. Anal. Calc. for C72H100P2PdS2Si7: C,
62.01; H, 7.23; S, 4.60. Found: C, 62.29; H, 7.48; S, 4.49%.
(75 MHz, C6D6)
d 1.21 (CH3), 1.36 (CH3), 1.90 (CH3), 21.33
(CH3ꢂ2), 26.12 (CH), 26.63 (CH), 30.17 (CH), 30.66 (CH3), 127.56
(CH), 128.17 (CH), 128.54 (CH), 129.32 (CH), 130.12 (C, dd,
1JCP = 22.2 Hz, 3JCP = 2.5 Hz), 130.69 (C, dd, 1JCP = 22.2 Hz,
3
3JCP = 2.5 Hz), 130.97 (C), 131.22 (CH, d, JCP = 3.7 Hz), 131.37 (CH,
3
4
d, JCP = 3.7 Hz), 131.44 (CH, d, JCP = 1.2 Hz), 131.68 (C), 132.25
4
(CH, d, JCP = 1.2 Hz), 132.55 (C), 135.23 [CH, d, AA0X pattern, 1/2
(2JCP + 4JCP) = 6.4 Hz], 135.69 [CH, d, AA0X pattern, 1/2
(2JCP + 4JCP) = 6.4 Hz], 136.36 (C), 143.19 (C), 145.07 (C), 149.98
(C), 150.39 (C); 29Si NMR (59 MHz, C6D6) d 1.7, 2.0, 5.3; 31P NMR
(120 MHz, C6D6) d 6.68 (d, with platinum satellites, 1JPPt = 3532 Hz,
2JPP = 21 Hz), 25.10 (d, with platinum satellites, JPPt = 3209 Hz,
1
2JPP = 21 Hz); HRMS (FAB+) m/z: calcd. for C72H100OP2196PtSSi7
1466.5004, found 1466.5013. Anal. Calc. for C72H100OP2PtSSi7: C,
58.94; H, 6.87; S, 2.19. Found: C, 58.90; H, 6.83; S, 2.12%.
4.12. Synthesis of [Tbt(Mes)Si(l-O)(l-Se)Pt(PPh3)2] (17c)
4.10. Synthesis of [Tbt(Mes)Si(l-S)2Pt(PPh3)2] (17a)
To solution of hydroxysilaneselenol 1c (47.3 mg,
a
To a solution of 1a (27.8 mg, 0.0363 mmol) in THF (3 mL) was
added n-BuLi (1.64 N hexane solution, 0.0510 mL, 0.0821 mmol)
at 0 °C. After the mixture was stirred at 0 °C for 30 min, a THF solu-
tion (15 mL) of cis-[PtCl2(PPh3)2] (43.1 mg, 0.0544 mmol) was
added. The pale yellow solution turned deep yellow. After the re-
moval of the solvent, benzene (3 mL) was added to the residue.
The mixture was filtrated through CeliteÒ, and the solvent was re-
moved under reduced pressure. The residue was separated with
GPLC (toluene) to afford 17a (50.5 mg, 0.0341 mmol, 94%) as a pale
yellow solid. Pale yellow crystals suitable for X-ray structural anal-
ysis were grown from hexane at ꢀ20 °C. 17a: pale yellow crystals,
m.p. 250 °C (dec.); 1H NMR (300 MHz, C6D6) d 0.21 (s, 18H), 0.29 (s,
18H), 0.34 (s, 18H), 1.49 (s, 1H), 2.11 (s, 1H), 2.31 (s, 3H), 2.53 (s,
1H), 2.93 (s, 6H), 6.50 (s, 1H), 6.62 (s, 1H), 6.83 (s, 2H), 6.85–6.94
(m, 18H, PPh3), 7.49–7.55 (m, 12H, PPh3); 13C{1H} NMR (75 MHz,
0.0594 mmol) in THF (3 mL) was added NaH (3.60 mg,
0.150 mmol) at 0 °C. After the mixture was stirred at 0 °C for
30 min, a THF solution (15 mL) of cis-[PtCl2(PPh3)2] (46.9 mg,
0.0593 mmol) was added, and the mixture was stirred for 30 min
at 0 °C and then for 1.5 h while being warmed up to room temper-
ature. After the removal of the solvent, hexane (5 mL) was added to
the residue. The mixture was filtrated through CeliteÒ, and the sol-
vent was removed under reduced pressure. The residue was
recrystallized from benzene at room temperature to give pure
17c (80.7 mg, 0.0533 mmol, 90%) as pale yellow crystals. 17c: pale
yellow crystals, m.p. 172 °C (dec.); 1H NMR (300 MHz, C6D6) d 0.15
(s, 18H), 0.22 (s, 36H), 1.49 (s, 1H), 2.41 (s, 3H), 2.58 (br, s, 3H), 2.73
(br, s, 3H), 6.48 (s, 1H), 6.60 (s, 1H), 6.76 (sꢂ2, 2H), 6.78–6.85 (m,
6H), 6.88–6.93 (m, 12H), 7.42–7.48 (m, 6H), 7.59–7.66 (m, 6H), o-
benzyl protons of the Tbt group could not be observed because of

T. Tanabe et al. / Journal of Organometallic Chemistry 694 (2009) 353–365
363
the overlap with those of the Mes group; 13C{1H} NMR (75 MHz,
C6D6) d 1.27 (CH3), 1.32 (CH3), 2.20 (CH3), 21.26 (CH3ꢂ2), 26.15
(CH), 27.31 (CH), 30.95 (CH), 31.87 (CH3), 127.53 (CH), 128.12
C
42H77O102RuSSi7 ([M+H]+) 927.3123, found 927.3120. Anal. Calc.
for C42H76ORuSSi7: C, 54.43; H, 8.27. Found: C, 54.14; H, 7.98%.
1
(CH), 128.53 (CH), 129.33 (CH), 129.9 (C, dd, JCP = 22.8 Hz,
4.15. Synthesis of [Tbt(Mes)Si(l-O)(l-Se)Ru(g
6-benzene)] (18c)
1
3
3JCP = 2.5 Hz), 130.21 (C, dd, JCP = 22.8 Hz, JCP = 2.5 Hz), 131.45
3
(C), 132.13 (C), 132.24 (CH, d, JCP = 2.9 Hz), 132.45 (C), 133.06
To a solution of 1c (66.7 mg, 0.0845 mmol) in THF (2 mL) was
added NaH (4.40 mg, 0.184 mmol) at 0 °C. After the mixture was
stirred at 0 °C for 30 min, a THF solution (25 mL) of [RuCl2(ben-
zene)]2 (25.3 mg, 0.0507 mmol) was added, and the pale yellow
solution turned deep brown. After the removal of the solvent, hex-
ane (10 mL) was added to the residue. The mixture was filtrated
through CeliteÒ, and the solvent was removed under reduced pres-
sure. The residue was separated with WCC (hexane:Et2O = 2:1) to
afford 18c (50.3 mg, 0.0516 mmol, 61%) as a deep blue solid. Deep
blue crystals suitable for X-ray structural analysis were grown
from benzene. 18c: deep blue crystals, m.p. 168 °C (dec.); 1H
NMR (300 MHz, C6D6) d 0.15 (s, 18H), 0.17 (s, 18H), 0.46 (s, 18H),
1.49 (s, 1H), 2.13 (s, 3H), 2.70 (s, 6H), 3.29 (s, 1H), 3.31 (s, 1H),
4.79 (s, 6H), 6.50 (s, 1H), 6.62 (s, 1H), 6.73 (s, 2H); 13C{1H} NMR
(75 MHz, C6D6) d 1.03 (CH3), 1.19 (CH3), 1.37 (CH3), 21.06 (CH3),
25.19 (CH3), 27.69 (CH), 27.97 (CH), 30.65 (CH), 76.25 (CH),
128.33 (CH), 128.54 (CH), 129.41 (CH), 132.56 (C), 137.12 (C),
138.20 (C), 142.64 (C), 143.94 (C), 150.82 (C), 151.15 (C); 77Se
NMR (95 MHz, C6D6) d 543.1; 29Si NMR (59 MHz, C6D6) d 1.9, 2.0,
2.8, 19.9; LRMS (FAB+) m/z: calcd. for C42H77O102Ru80SeSi7
([M+H]+) 975, found 975; HRMS (FAB+) m/z: calcd. for C42H77O102R-
3
4
(CH, d, JCP = 2.9 Hz), 133.85 (CH, d, JCP = 1.2 Hz), 134.42 (CH, d,
4JCP = 1.2 Hz), 135.29 [CH, d, AA0X pattern, 1/2 (2JCP + 4JCP) = 6.8 Hz],
135.69 [CH, d, AA0X pattern, 1/2 (2JCP + 4JCP) = 6.8 Hz], 136.51 (C),
143.48 (C), 145.60 (C), 152.09 (C), 152.44 (C); 29Si NMR (59 MHz,
C6D6) d ꢀ3.3, 1.7, 2.2; 77Se NMR (95 MHz, C6D6, 330 K) d 14.4
(1JSePt = 256 Hz, JSeP = 27 Hz); 31P NMR (120 MHz, C6D6) d 6.21 (d,
2
1
2
with platinum satellites, JPPt = 3537 Hz, JPP = 19 Hz), 24.67 (d,
1
2
with platinum satellites, JPPt = 3206 Hz, JPP = 19 Hz); HRMS
(FAB+) m/z: calcd. for C72H100OP2195Pt80SeSi7 1513.4448, found
1513.4446. Anal. Calc. for C72H100OP2PtSeSi7: C, 57.11; H, 6.66.
Found: C, 57.31; H, 6.66%.
4.13. Synthesis of [Tbt(Mes)Si(l-S)2Ru(g
6-benzene)] (18a)
To a solution of 1a (76.6 mg, 0.100 mmol) in THF (2 mL) was
added n-BuLi (1.64 N hexane solution, 0.124 mL, 0.200 mmol) at
0 °C. After the mixture was stirred at 0 °C for 30 min, a THF solution
(25 mL) of [RuCl2(benzene)]2 (25.0 mg, 0.0502 mmol) was added.
The pale yellow solution turned deep brown. After the removal
of the solvent, hexane (10 mL) was added to the residue. The mix-
ture was filtrated through CeliteÒ, and the solvent was removed
under reduced pressure. The residue was separated with WCC
(hexane:Et2O = 2:1) to afford 18a (69.0 mg, 0.0725 mmol, 72%) as
a deep green solid. Deep green crystals suitable for X-ray structural
analysis were grown from benzene. 18a: deep green crystals, m.p.
190 °C (dec.); 1H NMR (300 MHz, C6D6) d 0.21 (s, 18H), 0.30 (s,
18H), 0.32 (s, 18H), 1.50 (s, 1H), 2.02 (s, 3H), 2.85 (s, 6H), 3.03 (s,
1H), 3.12 (s, 1H), 4.71 (s, 6H), 6.52 (s, 1H), 6.64 (s, 1H), 6.69 (s,
2H); 13C{1H} NMR (75 MHz, C6D6) d 1.14 (CH3), 1.99 (CH3), 2.32
(CH3), 20.83 (CH3), 27.93 (CH3), 27.61 (CH), 30.35 (CH), 30.72
(CH), 78.56 (CH), 128.62 (CH), 128.91 (CH), 129.97 (CH), 133.16
(C), 136.98 (C), 137.91 (C), 143.41 (C), 144.16 (C), 151.59 (C),
152.98 (C); 29Si NMR (59 MHz, C6D6) d 1.9, 2.7, 44.1; LRMS
(FAB+) m/z: calcd. for C42H76102RuS2Si7 ([M]+) 942, found 942;
HRMS (FAB+) m/z: calcd. for C42H76102RuS2Si7 ([M]+) 942.2817,
found 942.2811. Anal. Calc. for C42H76RuS2Si7: C, 53.50; H, 8.12.
Found: C, 53.69; H, 8.34%.
u
80SeSi7 ([M+H]+) 975.2568, found 975.2573. Anal. Calc. for
C42H76ORuSeSi7: C, 51.81; H, 7.87. Found: C, 51.56; H, 8.05%.
4.16. Synthesis of [Tbt(Mes)Si(l-S)2Ru(PMe3)3] (19a)
To a solution of 18a (80.5 mg, 0.0854 mmol) in THF (3 mL) was
added PMe3 (1.0 [M] THF solution, 0.850 mL, 0.850 mmol) at room
temperature. After the mixture was stirred at the temperature for
10 min, the deep green solution turned deep red. After the removal
of the solvent under reduced pressure, the residue was recrystal-
lized from hexane to afford 19a (92.4 mg, 0.0845 mmol, 99%).
19a: red crystals, m.p. 202 °C (dec.); 1H NMR (300 MHz, C6D6) d
0.24 (s, 18H), 0.39 (s, 18H), 0.40 (s, 18H), 1.05 (m, 27H), 1.53 (s,
1H), 2.18 (s, 3H), 3.13 (s, 6H), 3.98 (s, 1H), 4.05 (s, 1H), 6.57 (s,
1H), 6.67 (s, 1H), 6.82 (s, 2H); 13C{1H} NMR (75 MHz, C6D6) d
1.33 (CH3), 2.44 (CH3), 2.72 (CH3), 20.94 (CH3), 21.28 (PMe3, m),
25.83 (CH), 26.02 (CH), 27.11 (CH3), 30.41 (CH), 123.81 (CH),
128.54 (C), 129.39 (CH), 129.99 (CH), 136.60 (C), 141.43 (C),
142.35 (C), 143.95 (C), 151.02 (C), 151.24 (C); 31P NMR
(120 MHz, C6D6) d 21.99; 29Si NMR (59 MHz, C6D6) d 1.8, 2.6,
31.1; LRMS (FAB+) m/z: calcd. for C45H97P3102RuS2Si7 ([M]+) 1092,
found 1092; HRMS (FAB+) m/z: calcd. for C45H97P3102RuS2Si7
([M]+) 1092.3673, found 1092.3684. Anal. Calc. for C45H97P3RuS2-
Si7: C, 49.45; H, 8.95; S, 5.87. Found: C, 49.72; H, 9.01; S, 5.61%.
4.14. Synthesis of [Tbt(Mes)Si(l-O)(l-S)Ru(g
6-benzene)] (18b)
To a solution of 1b (80.0 mg, 0.108 mmol) in THF (2 mL) was
added NaH (5.20 mg, 0.217 mmol) at 0 °C. After the mixture was
stirred at 0 °C for 30 min, a THF solution (25 mL) of [RuCl2(ben-
zene)]2 (29.6 mg, 0.0593 mmol) was added, and the pale yellow
solution turned deep brown. After the removal of the solvent, hex-
ane (10 mL) was added to the residue. The mixture was filtrated
through CeliteÒ, and the solvent was removed under reduced pres-
sure. The residue was separated with WCC (hexane:Et2O = 2:1) to
afford 18 b (51.9 mg, 0.0561 mmol, 52%) as a deep violet solid.
Deep violet crystals suitable for X-ray structural analysis were
grown from benzene. 18b: deep violet crystals, m.p. 195 °C
(dec.); 1H NMR (300 MHz, C6D6) d 0.17 (s, 18H), 0.20 (s, 36H),
1.49 (s, 1H), 2.12 (s, 3H), 2.71 (s, 6H), 3.24 (s, 1H), 3.29 (s, 1H),
4.80 (s, 6H), 6.48 (s, 1H), 6.61 (s, 1H), 6.74 (s, 2H); 13C{1H} NMR
(75 MHz, C6D6) d 1.02 (CH3), 1.17 (CH3), 23.00 (CH3), 25.26 (CH3),
27.19 (CH), 27.81 (CH), 30.63 (CH), 76.73 (CH), 128.54 (CH),
128.63 (CH), 129.35 (CH), 133.06 (C), 136.89 (C), 138.11 (C),
142.95 (C), 143.90 (C), 151.00 (C), 151.28 (C); 29Si NMR (59 MHz,
C6D6) d 1.9, 2.7, 25.2; LRMS (FAB+) m/z: calcd. for C42H77O102RuSSi7
([M+H]+) 927, found 927; HRMS (FAB+) m/z: calcd. for
4.17. Synthesis of [Tbt(Mes)Si(l-O)(l-S)Ru(PMe3)3] (19b)
To a solution of 18b (57.7 mg, 0.0606 mmol) in THF (3 mL) was
added PMe3 (1.0 [M] THF solution, 0.600 mL, 0.600 mmol) at room
temperature. After the mixture was stirred at the temperature for
10 min, the deep violet solution turned deep red. After the removal
of the solvent under reduced pressure, the residue was recrystal-
lized from hexane to afford 19 b (58.5 mg, 0.0543 mmol, 96%).
Red crystals suitable for X-ray structural analysis were grown from
benzene. 19b: red crystals, m.p. 208 °C (dec.); 1H NMR (300 MHz,
C6D6) d 0.23 (s, 18H), 0.25 (s, 18H), 0.48 (s, 18H), 1.08 (m, 27H),
1.52 (s, 1H), 2.22 (s, 3H), 2.95 (s, 6H), 4.14 (s, 1H), 4.15 (s, 1H),
6.56 (s, 1H), 6.66 (s, 1H), 6.81 (s, 2H); 13C{1H} NMR (75 MHz,
C6D6) d 1.39 (CH3), 2.39 (CH3), 2.69 (CH3), 21.00 (CH3), 20.58
(PMe3, m), 25.93 (CH), 25.79 (CH), 27.23 (CH3), 30.51 (CH),

364
T. Tanabe et al. / Journal of Organometallic Chemistry 694 (2009) 353–365
123.78 (CH), 128.66 (C), 129.40 (CH), 130.04 (CH), 136.72 (C),
141.49 (C), 142.57 (C), 143.93 (C), 151.05 (C), 151.44 (C); 31P
NMR (120 MHz, C6D6) d 26.52; 29Si NMR (59 MHz, C6D6) d 1.9,
2.7, 25.2; LRMS(FAB+) m/z: calcd. for C45H98OP3102RuSSi7
([M+H]+) 1077, found 1077; HRMS(FAB+) m/z: calcd. for
C45H98OP3102RuSSi7 ([M+H]+) 1077.3980, found 1077.3961.
17c, 18b and 18c. These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre via www.ccdc.cam.a-
c.uk/data_request/cif. Supplementary data associated with this
article can be found, in the online version, at doi:10.1016/
j.jorganchem.2008.11.001.
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Acknowledgements
This work was partially supported by Grants-in-Aid for Creative
Scientific Research (No. 17GS0207), Science Research on Priority
Areas (No. 19027024, ‘‘Synergy of Elements”), Young Scientist (B)
(Nos. 18750030), and the Global COE Program (B09, ‘‘Integrated
Material Science”) from Ministry of Education, Culture, Sports, Sci-
ence and Technology, Japan. T.T. thanks Research Fellowships of
the Japan Society for the Promotion of Science for Young Scientists
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mentary crystallographic data for 1a, 1b, 1c, 11, 12, 16, 17a, 17b,

T. Tanabe et al. / Journal of Organometallic Chemistry 694 (2009) 353–365
365
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