First structural characterization of silanedithiol and its application toward the synthesis of silanedithiolato complexes

Article abstract of DOI:10.1002/ejic.200601226

In this paper, we report the synthesis and the structural characterization of stable examples of silanedithiol [Tbt(Mes)Si(SH)₂ (1)], hydroxysilanethiol [Tbt(Mes)Si(OH)(SH) (3)], and hydroxysilaneselenol [Tbt(Mes)Si(OH)(SeH) (7)], which are kin

Full text of DOI:10.1002/ejic.200601226

SHORT COMMUNICATION
DOI: 10.1002/ejic.200601226
First Structural Characterization of Silanedithiol and Its Application toward
the Synthesis of Silanedithiolato Complexes
Taro Tanabe,[a] Nobuhiro Takeda,[a] and Norihiro Tokitoh*[a]
Keywords: Silanedithiol / Silanedithiolato complexes / Silaneselenol / Group 10 transition metal complexes / X-ray crystal-
lography
In this paper, we report the synthesis and the structural char-
acterization of stable examples of silanedithiol [Tbt(Mes)-
Si(SH)2 (1)], hydroxysilanethiol [Tbt(Mes)Si(OH)(SH) (3)],
and hydroxysilaneselenol [Tbt(Mes)Si(OH)(SeH) (7)], which
are kinetically stabilized by an effective combination of steric
protection groups, Tbt (2,4,6-tris[bis(trimethylsilyl)meth-
yl]phenyl) and Mes (2,4,6-trimethylphenyl). Silanedichalcog-
enols 1, 3, and 7 are suggested to exist as a monomer without
any intermolecular contact such as hydrogen bonds both in
the solid state and in solution as judged by X-ray structural
analysis and IR spectroscopy. Treatment of 1 with 2 equiv.
of butyllithium resulted in the quantitative formation of the
corresponding dilithium silanedithiolate, Tbt(Mes)Si(SLi)2
(8), the generation of which was confirmed by a trapping ex-
periment using MeI. Furthermore, the addition of cis-
[MCl2(PPh3)2] (M = Pd, Pt) to a THF solution of 8 afforded
the corresponding silanedithiolato complexes, [Tbt(Mes)Si(µ-
S)2M(PPh3)2] (9a: M = Pd; 9b: M = Pt), respectively.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2007)
could be easily converted into the heterodimetallic sulfido
clusters.[9] Thus, kinetic stabilization should be an appropri-
ate method for the stabilization of M(SH)2 species. In this
paper, we present the synthesis and the first structural char-
acterization of a silanedithiol, which is kinetically stabilized
by an effective steric protection group, Tbt. In addition,
its application as a building block toward the synthesis of
silanedithiolato complexes will also be presented.
Introduction
Controlled synthesis of (chalcogenido)metal clusters has
been one of the most attractive subjects in organometallic
chemistry.[1] Recently, silanethiolato or silanedithiolato
complexes of late transition metals have been shown to be
good precursors of (sulfido)mixed-metal clusters prepared
by ligand exchange involving Si–S bond cleavage.[2,3] How-
ever, chelating silanedithiolato complexes are less common
due to the limitation of appropriate synthetic methodology.
That is, an excess amount of 1,3,5,2,4,6-trithiatrisilinane
(SSiMe2)3 should be required as a sulfur transfer reagent
for the synthesis of such silanedithiolato complexes.[4] On
the other hand, silanedithiols, which should be a good pre-
cursor of silanedithiolato complexes, have attracted much
interest from the viewpoint of their structure and proper-
ties. However, it is very difficult to isolate silanedithiols due
to their high sensitivity toward moisture, and the properties
remained little understood.[5] As for the analogues of main
group elements having two geminal SH groups, three exam-
ples are structurally characterized, i.e., TbtB(SH)2,[6]
Results and Discussion
Silanedithiol 1 was synthesized by the reaction of the
corresponding sterically hindered tetrathiasilolane 2[10] with
1.5 equiv. of LiAlH4 at 0 °C as air- and moisture-stable
crystals in 83% isolated yield (Scheme 1). When the reac-
tion was carried out at room temperature, further reduction
occurred to give a mixture of 1, Tbt(Mes)Si(H)SH and
Tbt(Mes)SiH2.
[8]
AlL(SH)2,[7] and Dep(Dip)Ge(SH)2 {Tbt = 2,4,6-tris[bis-
(trimethylsilyl)methyl]phenyl,
L
(β-diketiminato)
=
[N(Dip)C(Me)]2CH, Dip = 2,6-diisopropylphenyl, Dep =
2,6-diethylphenyl}, where the reactive M–SH moieties are
protected by bulky substituents. All of these compounds
[a] Institute for Chemical Research, Kyoto University
Gokasho, Uji, Kyoto 611-0011, Japan
Fax: +81-774-38-3200
E-mail: tokitoh@boc.kuicr.kyoto-u.ac.jp
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
Scheme 1. Synthesis of 1.
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T. Tanabe, N. Takeda, N. Tokitoh
SHORT COMMUNICATION
Silanedithiol 1 is stable in [D6]benzene solution even in bonding in the solid state was suggested by the packing
the presence of H2O for 1 d, reflecting the extreme bulki- view, where the observed intermolecular distances between
ness of the combination of Tbt and Mes groups. However, chalcogen atoms are apparently longer than the sum of the
1 underwent ready hydrolysis during preparative thin layer van der Waals radii.[14]
chromatography (SiO2) to afford the corresponding hy-
droxysilanethiol 3 quantitatively (Scheme 2).
Scheme 2. Synthesis of 3 by hydrolysis of 1.
The successful isolation of silanedithiol 1 prompted us to
attempt the synthesis of the selenium analogue, silanedise-
lenol, a stable example of which has been unknown. Unfor-
tunately, tetraselenasilolane, the selenium analogue of 2, is
known to be not available.[10] Another synthetic route is re-
quired to obtain the heavier analogue. We focused our at-
tention on the (silanedichalcogenolato)zirconium com-
plexes, which possess reactive Zr–E (E = S, Se) bonds.
When disilene 5[10] was treated with Cp2ZrE5 at 60 °C, the
corresponding silanedichalcogenolato complexes 6a,b were
obtained.[11] Treatment of 6a with H2O followed by the sep-
Figure 1. Crystal structure of 1 (ORTEP plot; thermal ellipsoids
aration afforded 1, where the hydrolysis of the Zr–S bonds
should occur selectively. Thus, the SiS2Zr ring system (6a)
hydrogen atoms are omitted for clarity). Selected bond lengths [Å]
are shown at 50% probability; hydrogen atoms except for the S–H
was found to be another precursor for silanedithiol 1. The
selenium analogue 6b should be a good precursor for silane-
diselenol. However, the reaction of 6b with H2O gave hy-
droxysilaneselenol 7, which was probably formed by further
hydrolysis of the initially generated silanediselenol 4
(Scheme 3).
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).
The IR spectra in the solid state for 1, 3, and 7 show
sharp absorptions assigned to the E–H stretching vibrations
[1: 2572 cm–1; 3: 2661 cm–1, 3646 cm–1; 7: 2479 cm–1,
3656 cm–1], suggesting the absence of intra- and intermo-
lecular interactions through hydrogen bonds.[15] No change
of the IR spectra in CCl4 with several concentrations indi-
cated their monomeric structure and almost no intermo-
lecular contact even in solution.
The generation of dilithium silanedithiolate 8 in the reac-
tion of 1 with 2 equiv. of nBuLi was confirmed by a trap-
ping experiment with MeI. Compound 8 should be appli-
cable toward the development of a new synthetic strategy
for (silanedithiolato)transition-metal complexes. Addition
of cis-[MCl2(PPh3)2] (M = Pd, Pt) to a THF solution of 8
resulted in the almost quantitative formation of the corre-
sponding silanedithiolato complexes 9a,b, respectively
(Scheme 4).[16] The 29Si NMR signals of the central silicon
atoms in the silanedithiolato complexes 9a (δSi = 15.3 ppm)
Scheme 3. Reaction of 5 with Cp2ZrE5 (E = S, Se).
The molecular structures of the newly isolated silane- and 9b (δSi = 14.2 ppm), which appear in the characteristic
dichalcogenols, 1, 3, and 7, were fully determined by X-ray region of silanedithiolato complex signals,[4c] are in a lower-
crystallographic analysis (Figure 1).[12] To the best of our field region than that of 1 (δSi = –1.8 ppm). The structures
knowledge, these are the first examples of the X-ray struc- of 9a,b were revealed by X-ray crystallography. Both of the
tural analyses of a silanedithiol, a hydroxysilanethiol, and four-membered rings consisting of Si, S, and Pd or Pt atoms
a hydroxysilaneselenol.[13] The Si–E (E = O, S, Se) bond have puckered structures, though the SiS2Pd ring of the re-
lengths of 1, 3, and 7 are within the range of those reported ported (silanedithiolato)palladium complex, [Me2Si(µ-S)2-
for the corresponding single bonds between silicon and Pd(PEt3)2],[4c] has an almost planar structure. This is proba-
chalcogen atoms. Absence of intermolecular hydrogen bly due to the steric repulsion between the extremely bulky
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Silanedithiol and Its Applications
SHORT COMMUNICATION
ods and/or by an Ultimate Solvent System (Glass Contour Com-
pany).[18] C6D6 used as a solvent was dried with Na, then with a
K mirror. 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 (δ = 7.25 ppm) or C6D5H (δ = 7.15 ppm) as
an internal standard. 13C NMR (75 MHz) spectra were recorded
with a JEOL JNM AL-300 spectrometer. 13C chemical shifts are
reported in ppm downfield from tetramethylsilane and referenced
to the carbon signal of CDCl3 (δ = 77.0 ppm) or C6D6 (δ =
128.0 ppm). The multiplicity of signals in the 13C NMR spectra
was determined by the DEPT technique. The 29Si (59 MHz), 31P
(120 MHz), 77Se (95 MHz), and 195Pt (64 MHz) NMR spectra were
recorded with a JEOL JNM AL-300 spectrometer. IR spectra were
recorded with a JASCO FT/IR-5300 spectrometer. High- and low-
resolution mass spectrometric data were obtained with 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 with a Yanaco
micro melting point apparatus and are uncorrected. Wet column
chromatography (WCC) and preparative thin-layer chromatog-
raphy (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 Ana-
lytical Industry Co., Ltd. Systems) equipped with JAIGEL 1H and
2H columns (eluent: toluene).
Tbt group and the triphenylphosphane groups. The X-ray
structural analysis of 9b[17] is the first example of a silanedi-
thiolato complexes of platinum (Figure 2, Scheme 4).
Scheme 4. Synthesis of silanedithiolato complexes 9.
1: To a solution of 2 (165 mg, 238 µmol) in THF (15 mL) was
added LiAlH4 (13.5 mg, 356 µmol) at 0 °C. After the mixture was
stirred at 0 °C for 1 h, ethyl acetate (5 mL) was added. After re-
moval of the solvent, hexane was added to the residue. The suspen-
sion was filtered through Celite®, and the solvent was removed.
The residue was separated by silica gel chromatography (n-hexane)
to afford 1 (149.7 mg, 195.5 µmol, 83%); colorless crystals, m.p.
177–178 °C. 1H NMR (300 MHz, CDCl3): δ = –0.02 (s, 18 H), 0.00
(s, 18 H), 0.04 (s, 18 H), 1.18 (s, 2 H, S–H), 1.31 (s, 1 H), 2.22 (s,
3 H), 2.49 (s, 1 H), 2.57 (s, 6 H), 2.63 (s, 1 H), 6.24 (s, 1 H), 6.38
(s, 1 H), 6.76 (s, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 0.9
(q), 1.6 (q), 1.9 (q), 20.9 (q), 26.4 (q), 28.0 (d), 28.3 (d), 30.6 (d),
123.3 (d), 126.3 (s),128.5 (d), 130.5 (d), 134.9 (s), 139.7 (s), 142.8
(s), 145.5 (s), 151.9 (s), 152.2 (s) ppm. 29Si NMR (59 MHz, CDCl3):
Figure 2. Crystal structure of 9b·hexane (ORTEP plot; thermal el-
lipsoids are shown at 30% probability; hexane and 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).
δ = –1.8, 1.9, 2.9, 3.0 ppm. IR (KBr): ν = 2572 [ν(S–H)] cm–1.
˜
HRMS (FAB+): calcd. for C36H72S2Si7 [M]+ 764.3460, found
764.3472. C36H72S2Si7 (765.69): calcd. C 56.47, H 9.48, S 8.38;
found C 56.51, H 9.57, S, 8.81.
9b: To a solution of 1 (27.8 mg, 36.3 µmol) in THF (3 mL) was
added nBuLi (1.64  hexane solution, 51 µL, 82.1 µmol) at 0 °C.
After the mixture was stirred at 0 °C for 30 min, a THF solution
(15 mL) of cis-bis(triphenylphosphane)platinum dichloride
(43.1 mg, 54.4 µmol) was added. After removal of the solvent, ben-
zene (3 mL) was added to the residue. The mixture was filtered
through Celite®, and the solvent was removed. The residue was
separated with HPLC (toluene) to afford 9b (50.5 mg, 34.1 µmol,
Conclusions
We have succeeded in the synthesis and characterization
of a stable silanedithiol 1 and its application toward the
synthesis of the silanedithiolato complexes of palladium
and platinum. The stable silanedithiol should be a key spe-
cies as a building block for several types of (sulfido)mixed- 94%) as a pale yellow solid. Pale yellow crystals suitable for X-ray
structural analysis were grown from hexane at –20 °C; pale yellow
crystals, m.p. 250–252 °C (dec.). H NMR (300 MHz, C6D6): δ =
0.21 (s, 18 H), 0.29 (s, 18 H), 0.34 (s, 18 H), 1.49 (s, 1 H), 2.11 (s,
1 H), 2.31 (s, 3 H), 2.53 (s, 1 H), 2.93 (s, 6 H), 6.50 (s, 1 H), 6.62
(s, 1 H), 6.83 (s, 2 H), 6.85–6.94 (m, 18 H, Ph3P), 7.49–7.55 (m, 12
H, Ph3P) ppm. 13C{1H} NMR (75 MHz, C6D6): δ = 1.2 (CH3), 2.1
metal clusters. Further investigation on the reactivity of 8
and related compounds are currently in progress.
1
Experimental Section
(CH3), 2.5 (CH3), 21.1 (CH3), 25.3 (CH), 25.6 (CH), 26.9 (CH3),
4
General Procedure. All experiments were performed under anhy-
drous conditions under argon unless otherwise noted. All solvents
used in the reactions were purified prior to use by standard meth-
30.5 (CH), 127.8 (CH), 128.3 (CH), 128.5 (CH), 128.6 [d, JCP
=
3
1.2 Hz, CH, p-Ph(PPh3)], 131.41 [d, JCP = 1.9 Hz. CH, m-
Ph(PPh3)], 131.42 [dd, JCP = 54.9 Hz, JCP = 6.8 Hz, C, ipso-Ph
1
3
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T. Tanabe, N. Takeda, N. Tokitoh
SHORT COMMUNICATION
(PPh3)], 135.3 [AAЈX pattern, 1/2(2JCP
+
4JCP) = 5.5 Hz, CH, o-
[8]
a) T. Matsumoto, K. Tatsumi, Chem. Lett. 2001, 964–965; b)
T. Matsumoto, Y. Nakaya, K. Tatsumi, Organometallics 2006,
25, 4835–4845.
Such as TbtB(µ-S)2TiCp2, AlL(µ-S)2MCp2, and Dep(Dip)
Ge(µ-S)2Ru(η6-benzene) (Cp = C5H5, M = Ti, Zr), see refs.[6–8]
a) N. Tokitoh, H. Suzuki, R. Okazaki, J. Am. Chem. Soc. 1993,
115, 10428–10429; b) H. Suzuki, N. Tokitoh, R. Okazaki, Bull.
Chem. Soc. Jpn. 1995, 68, 2471–2481.
Recently, we reported the synthesis of (silanedichalcogenolato)-
titanium complexes by the reaction of a disilene 4 with
Cp2TiE5: N. Takeda, T. Tanabe, N. Tokitoh, Bull. Chem. Soc.
Jpn. 2006, 79, 1573–1579.
Ph (PPh3)], 136.6 (C), 137.9 (C), 141.9 (C), 143.1 (C), 143.3 (C),
151.3 (C), 151.6 (C) ppm. 29Si NMR (59 MHz, C6D6): δ = 1.6, 2.5,
14.1 ppm. 31P NMR (120 MHz, C6D6): δ = 21.2 (s, with platinum
[9]
1
satellites, JPPt = 3047 Hz) ppm. 195Pt NMR (64 MHz, C6D6,
[10]
1
Na2PtCl4): δ = –4527.7 (t, JPtP = 3047 Hz) ppm. UV/Vis (n-hex-
ane): λmax = 290 (br., ε = 4ϫ104), 269 (br., ε = 6ϫ104), 232 (br.,
ε = 1ϫ105), 209 (ε = 2ϫ105) nm. HRMS (FAB+): calcd. for
[11]
[12]
C72H100P2195PtS2Si7
[M]+
1481.4774,
found
1481.4771.
C72H100P2PtS2Si7 (1483.32): calcd. C 58.30, H 6.80, S 4.32; found
C 58.39, H 6.89, S 4.31.
Crystal data for 1: The intensity data were collected with a
Rigaku/MSC Mercury CCD diffractometer with graphite-mo-
nochromated Mo-Kα radiation (λ = 0.71070 Å). The structures
were solved by direct methods (SIR-97) and refined by full-
matrix least-squares procedures on F2 for all reflections
(SHELXL-97). Formula C36H72S2Si7, MW = 765.69; triclinic;
Supporting Information (see footnote on the first page of this arti-
cle): Experimental procedures, spectroscopic data, and crystal data
of 3, 7, 9a and 9b.
¯
space group P1 (#2); a = 9.2535(4), b = 15.9925(5), c =
Acknowledgments
15.8055(7) Å; α = 82.9726(15), β = 81.7950(17), γ = 81.365(4)°;
V = 2276.62(16) Å3; Z = 2; µ = 0.324 mm–1; Dcalcd.
=
This work was supported in part by Grants-in-Aid for Creative
Scientific Research (17GS0207), Scientific Research on Priority
Area (No. 14078213), COE Research on Elements Science (No.
12CE2005), and the 21st Century COE Program, Kyoto University
Alliance for Chemistry, from the Ministry of Education, Culture,
Sports, Science and Technology, Japan. We are grateful to Dr. Tak-
ahiro Sasamori, Institute for Chemical Research, Kyoto University,
for the valuable discussions.
1.117 gcm–3; 2θmax = 51.0°; T = 103(2) K; R1 [IϾ2σ(I)] =
0.0563; wR2 (all data) = 0.1350; GOF = 1.049 for 8315 reflec-
tions and 427 parameters. CCDC-627421 (1) contains the sup-
plementary crystallographic data for this paper. These data can
be obtained free of charge from The Cambridge Crystallo-
graphic Data Center via www.ccdc.cam.ac.uk/data_request/cif.
Crystal data for 3 and 7 are given in the Supporting Infor-
mation. CCDC-627422 (3) and -627425 (7) contain the supple-
mentary crystallographic data for this paper. These data can
be obtained free of charge from The Cambridge Crystallo-
graphic Data Center via www.ccdc.cam.ac.uk/data_request/cif.
We have already reported the synthesis of the stable si-
lanethione and silaneselone, Tbt(Tip)Si=Ch (Ch = S, Se; Tip
= 2,4,6-triisopropylphenyl). They should be related compounds
to compounds 1, 3, and 7, since the hydrolyzed products of
the silanethione and silaneselone are Tbt(Tip)Si(OH)(SH) and
Tbt(Tip)Si(OH)(SeH), which have already been reported. For
reviews on heavy ketones, see: R. Okazaki, N. Tokitoh, Acc.
Chem. Res. 2000, 33, 625–630.
[13]
[1] For reviews, see; a) D. Coucouvanis, Acc. Chem. Res. 1991, 24,
1–8; b) H. Weller, Angew. Chem. Int. Ed. Engl. 1993, 32, 41–
53; c) M. Hidai, S. Kuwata, Y. Mizobe, Acc. Chem. Res. 2000,
33, 46–52.
[2] a) L. Cai, R. H. Holm, J. Am. Chem. Soc. 1994, 116, 7177–
7178; b) D. T. T. Tran, N. J. Taylor, J. F. Corrigan, Angew.
Chem. Int. Ed. 2000, 39, 935–937; c) P. A. Shapely, H.-C. Li-
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Int. Ed. 2003, 42, 465–468.
[15] The absorptions assignable to the E–H (E = O, S, Se) vi-
[3] T. Komuro, T. Matsuo, H. Kawaguchi, K. Tatsumi, Chem.
Commun. 2002, 988–989.
brations with E–H–E hydrogen bonding should be broadened
and shifted to lower wavenumbers. For example,
[Ru(SH2)(PPh3)‘S4’] shows one broad band for ν(S–H···S) at
2300 cm–1(KBr): D. Sellmann, P. Lechner, F. Knoch, M. Moll,
J. Am. Chem. Soc. 1992, 114, 922–930.
[4] a) D. M. Giolando, T. B. Rauchfuss, G. M. Clark, Inorg. Chem.
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[5] There are only few reports on dialkyl- or diarylsilanedithiols.
Dimethylsilanedithiol has been characterized only by IR spec-
troscopy due to its extreme instability: G. Gattow, H. P. De-
wald, Z. Anorg. Allg. Chem. 1991, 604, 63–67. As for diphenyl-
silanedithiol, only the boiling point has been reported: Y. Cai,
B. P. Roberts, Tetrahedron Lett. 2001, 42, 763–766. Syntheses
and some reactions of several dialkoxysilanedithiols have been
reported: a) W. Wojnowski, M. Wojnowska, Z. Anorg. Allg.
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[16] For the experimental procedure, spectral and crystal data for
9a, see the Supporting Information. CCDC-627423 (9a) con-
tains the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cambridge
Crystallographic Data Center via www.ccdc.cam.ac.uk/data_
request/cif.
[17] Crystal data for 9b (9b·hexane): Formula C78H114P2PtS2Si7,
¯
MW = 1569.47; triclinic; space group P1 (#2); a = 13.7853(8),
b = 16.8910(9), c = 21.0444(17) Å; α = 113.276(7), β =
102.504(4), γ = 92.842(3)°; V = 4344.4(5) Å3; Z = 2; µ =
1.833 mm–1; Dcalcd. = 1.200 Mg/m3; 2θmax = 50.0°; T = 173(2)
K; R1 [IϾ2σ(I)]
= 0.0511; wR2 (all data) = 0.1272;
GOF = 1.078 for 15211 reflections and 870 parameters.
CCDC-627424 (9b) contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Center via
www.ccdc.cam.ac.uk/data_request/cif.
[6] a) N. Tokitoh, M. Ito, R. Okazaki, Organometallics 1995, 14,
4460–4462; b) M. Ito, N. Tokitoh, R. Okazaki, Organometallics
1997, 16, 4314–4319.
[7] a) V. Jancik, Y. Peng, H. W. Roesky, J. Li, D. Neculai, A. M.
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[18] A. B. Pangborn, M. A. Giardello, R. H. Grubbs, R. K. Rosen,
F. J. Timmers, Organometallics 1996, 15, 1518–1520.
Received: December 22, 2006
Published Online: February 13, 2007
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Eur. J. Inorg. Chem. 2007, 1225–1228