σ-Acetylide complexes of ruthenium(IV) and osmium(IV) thiolates

Article abstract of DOI:10.1021/om011019t

Treatment of [M(Sxylyl)₃(MeCN)Cl] (M = Ru, Os; xylyl = 2,6-dimethylphenyl) with PhC≡CH in the presence of Et₃N afforded [Et₃NH][M(Sxylyl)₃(C≡CPh)-Cl]. The crystal structure of [Et₃NH][Ru(Sxylyl)₃(C≡Ctol)Cl] (tol = 4-tolyl) has been determined. The average Ru-S, Ru-C, and Ru-Cl distances are 2.1980, 1.991-(5), and 2.5131(13) ?, respectively. Interaction of [Et₄-NH][Ru(Sxylyl)₃(C≡CPh)Cl] with excess t-BuNC gave trans-[Ru(t-BuNC)₄(Sxylyl)₂].

Full text of DOI:10.1021/om011019t

Organometallics 2002, 21, 4017-4020
4017
σ-Acetylid e Com p lexes of Ru th en iu m (IV) a n d
Osm iu m (IV) Th iola tes
Qian-Feng Zhang,† Chui-Ying Lai,† Wai-Yeung Wong,‡ and Wa-Hung Leung*,†
Department of Chemistry and Open Laboratory of Chirotechnology of the Institute of
Molecular Technology for Drug Discovery and Synthesis, The Hong Kong University of Science
and Technology, Clear Water Bay, Kowloon, Hong Kong, China, and Department of Chemistry,
Hong Kong Baptist University, Waterloo Road, Kowloon Tong, Hong Kong, China
Received November 27, 2001
Summary: Treatment of [M(Sxylyl)3(MeCN)Cl] (M ) Ru,
Os; xylyl ) 2,6-dimethylphenyl) with PhCtCH in the
presence of Et3N afforded [Et3NH][M(Sxylyl)3(CtCPh)-
Cl]. The crystal structure of [Et3NH][Ru(Sxylyl)3(Ct
Ctol)Cl] (tol ) 4-tolyl) has been determined. The average
Ru-S, Ru-C, and Ru-Cl distances are 2.1980, 1.991-
(5), and 2.5131(13) Å, respectively. Interaction of [Et4-
NH][Ru(Sxylyl)3(CtCPh)Cl] with excess t-BuNC gave
trans-[Ru(t-BuNC)4(Sxylyl)2].
of these complexes feature the characteristic trigonal-
planar [M(SAr)3]+ core that is also found for the iso-
electronic Mo(II),9 Tc(III),10 and Re(III)11 analogues.
Interestingly, [M(SAr)4(MeCN)] reacted with CO to give
[M(SAr)4(CO)]. Therefore, one may expect that the
electron-rich {Ru(SAr)3}+ core should exhibit rich or-
ganometallic chemistry. Nevertheless, relatively few
organometallic compounds of Ru(IV) thiolates are known
to date.6d,7c,12,13 Herein we report the synthesis and
characterization of the first σ-acetylide complexes of
Ru(IV) and Os(IV) thiolates.
In tr od u ction
Transition-metal-sulfur systems are of significance
due to their central roles in biology1 and heterogeneous
catalysis.2 Of interest are binary sulfides of noble
metals, notably Ru, which are active catalysts for the
industrially important hydrodesulfurization process.3
Recently, molecular Ru thiolato and sulfido complexes
have also been synthesized to model the active sites of
metal-sulfide catalysts4 and metalloenzymes.5 While
Ru(II) thiolate complexes are well documented, the
analogous Ru(IV) system has received relatively less
attention.6-8 Trigonal-bipyramidal Ru(IV) and Os(IV)
thiolate complexes [M(SAr)4(MeCN)] (M ) Ru, Os; Ar
) aryl group such as 2,4,5,6-tetramethylphenyl and
2,4,6-triisopropylphenyl) were first synthesized by Koch
and Millar and co-workers.7a The solid-state structures
Resu lts a n d Discu ssion
Millar and Koch and co-workers synthesized [Ru-
(SAr)3(MeCN)] by reaction of [Et4N][RuCl4(MeCN)2]
with LiSAr in the presence of Ar2S2 in refluxing EtOH/
MeCN.7a We found that reaction of [Et4N][RuCl4-
(MeCN)2] with NaSxylyl (xylyl ) 2,6-dimethylphenyl)
afforded [Ru(Sxylyl)4(MeCN)] (1) along with [Et4N]-
[Ru(Sxylyl)4Cl] (2); the latter has been characterized by
X-ray diffraction. As previously reported,7d protonation
of 1 with HCl afforded [Ru(Sxylyl)3(MeCN)Cl] (3) in good
yield. The solid-state structures of 2 and 3 are shown
in Figures 1 and 2, respectively. Similar to [Ru(SAr)4-
(MeCN)],7a the geometry around Ru in complexes 2 and
3 is trigonal-bipyramidal with the equatorial thiolate
ligands adopting a “two-up one-down” conformation,
which can be explained in terms of the π interaction
between 3pπ orbitals the two equatorial sulfurs and the
* To whom correspondence should be addressed. E-mail:
chleung@ust.hk.
† Hong Kong University of Science and Technology.
empty 2e (dxy, dx -y ) Ru orbitals.7b The 1H NMR spectra
of 2 and 3 in CDCl3 show two sets of methyl resonance
signals, indicating that the two-up one-down conforma-
tion is maintained in solution. In 2, the Ru-S(equato-
2
2
‡ Hong Kong Baptist University.
(1) (a) Chan, M. K.; Kim, J . Rees, D. C. Science 1993, 260, 792. (b)
Beinert, H.; Holm, R. H.; Mu¨nck, E. Science 1997, 277, 653.
(2) Stiefel, E. I. In Transition Metal Sulfur Chemistry; Stiefel, E. I.,
Matsumoto, K., Eds.; American Chemical Society: Washington, DC,
1996; p 2, and references therein.
(3) (a) Chianelli, R. R.; Daage, M.; Ledoux, M. J . Adv. Catal. 1994,
40, 177. (b) Topsøe, H.; Clausen, B. S.; Massoth, F. E. Hydrotreating
Catalysis: Science and Technology; Springer Verlag: Berlin, 1996. (c)
Kabe, T.; Ishihara, A.; Qian, W. Hydrodesulfurization and Hydrodeni-
trogenation: Chemistry and Engineering; Wiley-VCH: Weinheim,
Germany, 1999. (d) Wojciechowska, M.; Pietrowski, M.; Lomnicki, S.
Chem. Commun. 1999, 463.
(4) Hidai, M.; Kuwata, S.; Mizobe, Y. Acc. Chem. Res. 2000, 33, 46.
(5) (a) Sellmann, D.; Sutter, J . Acc. Chem. Res. 1997, 30, 460. (b)
Sellmann, D.; Fu¨rsattel, A. Angew. Chem., Int. Ed. 1999, 38, 2023. (c)
Sellmann, D.; Fu¨rsattel, A.; Sutter, J . Coord. Chem. Rev. 2000, 200,
545.
(6) (a) Mattson, B. M.; Pignolet, L. H. Inorg. Chem. 1977, 16, 488.
(b) Kawano, M.; Uemura, H.; Watanabe, T.; Matsumoto, K. J . Am.
Chem. Soc. 1993, 115, 2068. (c) Mochizuk, K.; Kesting, F.; Weyher-
mu¨ller, T.; Wieghardt, K.; Butzlaff, C.; Trautwein, A. X. J . Chem. Soc.,
Chem. Commun. 1994, 909. (d) Belchem, G.; Steed, J . W.; Tocher, D.
A. J . Chem. Soc., Dalton Trans. 1994, 1949. (e) Sellmann, D.; Ruf, R.;
Knoch, F.; Moll, M. Inorg. Chem. 1995, 34, 4745. (f) Maiti, R.; Shang,
M.; Lappin, A. G. Chem. Commun. 1999, 2349.
(7) (a) Koch, S. A.; Millar, M. J . Am. Chem. Soc. 1983, 105, 3362.
(b) Millar, M. M.; O’Sullivan, T.; de Vries, N.; Koch, S. A. J . Am. Chem.
Soc. 1985, 107, 3714. (c) Soong, S. -L.; Hain, J . H., J r.; Millar, M.; Koch,
S. A. Organometallics 1988, 7, 556. (d) Satsangee, S. P.; Hain, J . H.,
J r.; Cooper, P. T.; Koch, S. A. Inorg. Chem. 1992, 31, 5160.
(8) (a) Dilworth, J . R.; Hu, J . Adv. Inorg. Chem. 1994, 33, 411. (b)
Torrens, H. Coord. Chem. Rev. 2000, 196, 331.
(9) Dilworth, J . R.; Hutchinson, J .; Zubieta, J . A. J . Chem. Soc.,
Chem. Commun. 1983, 1034.
(10) Blower, P. J .; Dilworth, J . R. J . Chem. Soc., Dalton Trans. 1985,
2305.
(11) De Vries, N.; Dewan, J . C.; J ones, A. G.; Davison, A. Inorg.
Chem. 1988, 27, 1574.
(12) Hidai, M.; Mizobe, Y. In Transition Metal Sulfur Chemistry,
Stiefel, E. I., Matsumoto, K., Eds.; American Chemical Society:
Washington, DC, 1996; p 310.
(13) (a) Leung, W.-H.; Lau, K.-K. Zhang, Q.-F.; Wong, W.-T.; Tang,
B. Organometallics 2000, 19, 2084. (b) Zhang, Q.-F.; Cheung, F. K.
M.; Wong, W.-Y.; Williams, I. D.; Leung, W.-H. Organometallics 2001,
20, 3777.
10.1021/om011019t CCC: $22.00 © 2002 American Chemical Society
Publication on Web 08/16/2002

4018 Organometallics, Vol. 21, No. 19, 2002
Notes
F igu r e 3. Molecular structure of the anion [Ru(Sxylyl)3-
(CtCtol)Cl]-. Selected bond lengths (Å) and angles (deg):
Ru(1)-S(1) ) 2.1999(12), Ru(1)-S(2) ) 2.1938(12), Ru(1)-
S(3) ) 2.2003(12), Ru(1)-C(1) ) 1.991(5), Ru(1)-Cl(1) )
2.5131(13), C(1)-C(2) ) 1.180(7); C(1)-Ru(1)-S(2) )
85.12(12), C(1)-Ru(1)-S(1) ) 93.10(12), S(2)-Ru(1)-S(1)
) 119.10(5), C(1)-Ru(1)-S(3) ) 94.01(12), S(2)-Ru(1)-
S(3) ) 117.78(5), S(1)-Ru(1)-S(3) ) 123.06(6), C(1)-
Ru(1)-Cl(1) ) 177.00(12), S(2)-Ru(1)-Cl(1) ) 97.51(4),
S(1)-Ru(1)-Cl(1) ) 84.37(5), S(3)-Ru(1)-Cl(1) ) 86.05(4),
C(2)-C(1)-Ru(1) ) 177.8(4).
Figu r e 1. Molecular structure of the anion [Ru(Sxylyl)4Cl]-.
Selected bond lengths (Å) and angles (deg): Ru(1)-S(1) )
2.1946(11), Ru(1)-S(2)
2.3986(10), Ru(1)-S(4)
)
)
2.2003(12), Ru(1)-S(3)
2.2161(12), Ru(1)-Cl(1)
)
)
2.4369(10); S(1)-Ru(1)-S(2) ) 117.59(5), S(1)-Ru(1)-S(4)
) 123.11(5), S(2)-Ru(1)-S(4) ) 119.18(5), S(1)-Ru(1)-
S(3) ) 84.23(5), S(2)-Ru(1)-S(3) ) 95.24(4), S(4)-Ru(1)-
S(3) ) 87.44(4), S(1)-Ru(1)-Cl(1) ) 93.13(4), S(2)-Ru(1)-
Cl(1) ) 83.97(4), S(4)-Ru(1)-Cl(1) ) 95.90(4), S(3)-
Ru(1)-Cl(1) ) 176.53(5).
4-tolylacetylene in the presence of Et3N afforded [Et3-
NH][Ru(Sxylyl)3(CtCtol)Cl] (5), which has been char-
acterized by X-ray crystallography (Figure 3). Similarly,
the Os analogue [Et3NH][Os(Sxylyl)3(CtCPh)Cl] (6)
was prepared from [Os(Sxylyl)3(MeCN)Cl]14 and PhCt
CH in the presence of Et3N. It may be noted that
structurally characterized Ru(IV) σ-acetylides are rather
rare.14 The structure of the anion [Ru(Sxylyl)3(Ct
Ctol)Cl]- consists of the trigonal {Ru(Sxylyl)3} core with
the chloride and acetylide at the axial positions. The
average Ru-S distance (2.1980 Å) in 5 is similar to that
in 3. The Ru-Cl distance (2.5131(13) Å) in 5 is longer
than those in 2 and 3, indicative of the order of trans
influence PhCtC- > xylylS- > MeCN. The ethynyl
moiety is almost linear (Ru-CR-Câ ) 177.8(4)°). The
Ru-CR distance of 1.991(5) Å is similar to that in
[Cp*RuH(CtCCO2Me)(dippe)][BPh4] (2.04(2) Å; dippe
) 1,2-bis(diisopropylphosphino)ethane).15
Treatment of 4 with 1 equiv of t-BuNC led to the
formation of a yellowish green solid, characterized as
[Ru(Sxylyl)3(t-BuNC)Cl] (7). When an excess of t-BuNC
(>4 equiv) was used, 4 was reduced to the Ru(II)
complex trans-[Ru(t-BuNC)4(Sxylyl)2] (8). Complex 8
could also be synthesized directly from 1 and excess
t-BuNC. The reaction mixture of 4 and t-BuNC was
found to contain 1,4-diphenylbutadiyne, identified by
13C NMR and IR analyses, suggesting that coupling of
the acetylide ligands had occurred. The molecular
structure of complex 8 is shown in Figure 4. The
geometry around Ru is pseudo-octahedral with two
mutually trans t-BuNC ligands. The Ru-S bond lengths
(average 2.4493 Å) in 8 are obviously longer than those
in 2, 3, and 5, indicative of the absence of Ru-S π
bonding. The average Ru-C distances in 8 of 1.9965 Å
are similar to those in related Ru(II) isocyanide
F igu r e 2. Molecular structure of [Ru(Sxylyl)3(MeCN)Cl]
(3). Selected bond lengths (Å) and angles (deg): Ru(1)-
S(1) ) 2.2072(8), Ru(1)-S(2) ) 2.1984(8), Ru(1)-S(3) )
2.2012(8), Ru(1)-N(1) ) 2.037(2), Ru(1)-Cl(1) ) 2.3643(8);
N(1)-Ru(1)-S(2) ) 86.25(7), N(1)-Ru(1)-S(3) ) 92.33(7),
S(2)-Ru(1)-S(3) ) 119.00(3), N(1)-Ru(1)-S(1) ) 94.51(7),
S(2)-Ru(1)-S(1) ) 116.87(3), S(3)-Ru(1)-S(1) ) 124.01(3),
N(1)-Ru(1)-Cl(1) ) 176.04(7), S(2)-Ru(1)-Cl(1) ) 96.64(3),
S(3)-Ru(1)-Cl(1) ) 83.91(3), S(1)-Ru(1)-Cl(1) ) 86.61(3).
rial) bond distances (average of 2.2037 Å) are shorter
than the Ru-S(axial) distance (2.3986(10) Å), indicative
of Ru-S(equatorial) π bonding. The average Ru-S
(2.2022 Å) and Ru-N (2.037(2) Å) distances in 3 are
comparable to those in [Ru(SAr)4(MeCN)] (Ar ) 2,3,5,6-
tetramethylphenyl) (2.209 and 2.096(5) Å, respectively7a).
The Ru-Cl distance in 2 (2.4369(10) Å) is slightly longer
than that in 3 (2.3643(8) Å), indicative of the trans
influence of the thiolate ligand.
Treatment of 2 with PhCtCH in CH2Cl2 resulted in
the formation of [Et4N][Ru(Sxylyl)3(CtCPh)Cl] (4),
which shows νCtC at 2052 cm-1 in the IR spectrum. No
reactions were found between 2 and alkylacetylenes
such as Me3SiCtCH or t-BuCtCH. Reaction of 3 with
(14) [Os(Sxylyl)3(MeCN)Cl] was prepared by the reaction of [NH4]2-
[OsCl6] with 2,6-dimethylthiophenol in the presence of Et3N in EtOH/
MeCN and purified by column chromatography (yield 46%).
(15) de los Rios, I.; Tenorio, M. J .; Puerta, M. C.; Valerga, P. J . Am.
Chem. Soc. 1997, 119, 6529.

Notes
Organometallics, Vol. 21, No. 19, 2002 4019
Ta ble 1. Cr ysta llogr a p h ic Da ta a n d Exp er im en ta l Deta ils for 2‚CH2Cl2, 3, 5, a n d 8‚2H2O
2‚CH2Cl2
3
5
8‚2H2O
formula
C
41H58Cl3NRuS4
C
26H30ClNRuS3
C
39H50ClNRuS3
C
36H58N4O2RuS2
fw
900.54
589.21
765.50
744.05
a, Å
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
Z
13.4154(8)
15.7625(9)
21.157(1)
11.0214(8)
15.219(1)
16.421(1)
11.3258(7)
15.619(1)
22.317(2)
9.2197(7)
9.9086(7)
12.3324(9)
108.901(1)
100.538(1)
97.534(1)
1025.7(1)
1
102.148(1)
98.347(1)
4473.8(4)
4
2692.6(3)
4
3906.0(4)
4
cryst syst
space group
orthorhombic
P212121
1.337
293(2)
0.745
monoclinic
P21/n
1.453
293(2)
0.929
monoclinic
P21/c
1.302
293(2)
0.657
triclinic
P1
1.205
293(2)
0.516
F
calcd, g cm-3
T, K
µ, mm-1
F(000)
1880
1208
1600
394
no. of rflns measd
no. of indep rflns
Rint
26478
10115
0.0475
0.0385, 0.0853
0.0817, 0.1030
0.762
15677
6079
0.0311
0.0335, 0.0742
0.0610, 0.0829
0.946
22488
8642
0.0387
0.0528, 0.1475
0.0911, 0.1883
0.896
5940
5114
0.0098
0.0368, 0.1026
0.0371, 0.1035
1.050
R1,a wR2b (I > 2.0σ(I))
R1, wR2 (all data)
GOFcon F2
R1 ) (∑|Fo| - |Fc|)/∑|Fo|. wR2 ) [(∑w(Fo - Fc2)2/∑w|Fo | ]1/2
.
c GOF ) [(∑w|Fo| - |Fc|)2/(Nobservns - Nparams)]1/2
.
a
b
2
2 2
[Ru(t-BuNC)4(Sxylyl)2]. A preliminary study showed
that [M(Sxylyl)3(CtCPh)Cl]- is capable of catalyzing
ring-opening metathesis polymerization of norbornene.
The investigation into the catalytic activity of these
σ-acetylide complexes is under way.
Exp er im en ta l Section
Gen er a l Con sid er a tion s. Solvents were purified by stan-
dard procedures and distilled prior to use. All manipulations
were carried out under nitrogen using standard Schlenk
techniques. [Et4N][RuCl4(MeCN)2] was prepared according to
a literature method.18 2,6-Dimethylthiophenol (xylylSH) and
1
t-BuNC were purchased from Aldrich. H NMR spectra were
recorded on a Bruker ARX 300 spectrometer operating at 300
MHz. Chemical shifts (δ, ppm) were reported with reference
to SiMe4. Infrared spectra were recorded on a Perkin-Elmer
16 PC FT-IR spectrophotometer, and mass spectra were
obtained on a Finnigan TSQ 7000 spectrometer. Elemental
analyses were performed by Medac Ltd, Surrey, U.K.
F igu r e 4. Molecular structure of trans-[Ru(t-BuNC)4-
(Sxylyl)2] (8). Selected bond lengths (Å) and angles (deg):
Ru(1)-S(1) ) 2.4558(7), Ru(1)-S(2) ) 2.4427(9), Ru(1)-
C(17) ) 2.054(2), Ru(1)-C(22) ) 1.987(4), Ru(1)-C(27) )
1.917(4), Ru(1)-C(32) ) 2.028(3); C(27)-Ru(1)-C(22) )
84.77(16), C(27)-Ru(1)-C(32) ) 95.24(16), C(22)-Ru(1)-
C(32) ) 179.45(15), C(27)-Ru(1)-C(17) ) 179.70(16),
C(22)-Ru(1)-C(17) ) 95.43(13), C(32)-Ru(1)-C(17) )
P r ep a r a tion s of [Ru (Sxylyl)4(MeCN)] (1) a n d [Et4N]-
[Ru (Sxylyl)4Cl] (2). This was synthesized by a modification
of the literature method. To a slurry of [Et4N][RuCl4(MeCN)2]
(511 mg, 1.25 mmol) in MeOH/MeCN (2:1, 50 mL) were added
2,6-dimethylthiophenol (863 mg, 6.25 mmol) and NaOMe (338
mg, 6.25 mmol), and the mixture was heated at reflux for 8 h
and then cooled at room temperature. After removal of solvents
under vacuum, the brown crude product was washed with
hexane and Et2O and then was extracted with CHCl3. Et2O
was layered on the concentrated extract, and the mixture was
cooled to -10 °C, giving 1 as dark brown crystals (457 mg,
53%). Further recrystallization of the dark residue from CH2-
Cl2/EtOH/Et2O afforded green-brown crystals of 2 (366 mg,
26%). Complex 2 could also be purified by column chromatog-
raphy (silica gel) using CH2Cl2/acetone (2:1, v/v) as eluant.
Data for 1 are as follows. 1H NMR (CDCl3): δ 7.34 (t, 1H, Hp),
7.29 (t, 1H, Hp), 7.22 (t, 2H, Hp), 7.15 (d, 2H, Hm), 7.08 (d, 2H,
Hm), 6.99 (d, 4H, Ho), 2.21 (s, 18H, Me), 2.09 (s, 6H, Me), 1.98
(s, 3H, MeCN). MS (FAB): m/z 692 (M+ + 1), 650 ([Ru(Sxylyl)4]
+ 1), 512 ([Ru(Sxylyl)3]), 375 ([Ru(Sxylyl)2]). Anal. Calcd for
84.56(12), C(27)-Ru(1)-S(2)
)
85.22(10), C(22)-
Ru(1)-S(2) ) 87.42(10), C(32)-Ru(1)-S(2) ) 92.03(9),
C(17)-Ru(1)-S(2) ) 95.01(7), C(27)-Ru(1)-S(1) ) 94.31-
(10), C(22)-Ru(1)-S(1) ) 92.56(10), C(32)-Ru(1)-S(1) )
87.99(9), C(17)-Ru(1)-S(1) ) 85.46(7), S(2)-Ru(1)-S(1)
) 179.54(4).
complexes: e.g., trans-[Ru{N(i-Pr2PS)2}2(t-BuNC)2]
(1.990(3) Å)16 and trans-[Ru(S2CNEt2)2(t-BuNC)2]
(1.997(2) Å).17
In summary, the first σ-acetylide complexes of Ru(IV)
and Os(IV) thiolates [M(Sxylyl)3(CtCPh)Cl]- have been
synthesized from [M(Sxylyl)3(MeCN)Cl] (M ) Ru, Os)
and PhCtCH in the presence of Et3N. [Ru(Sxylyl)3-
(CtCPh)Cl]- was reduced by t-BuNC to give trans-
C
34H39NRuS4: C, 59.10; H, 5.69; N, 2.03. Found: C, 58.76; H,
1
5.61; N, 2.01. Data for 2 are as follows. H NMR (CDCl3): δ
7.32 (t, 1H, Hp), 7.27 (t, 1H, Hp), 7.21 (t, 2H, Hp), 7.13 (d, 2H,
Hm), 7.05 (d, 2H, Hm), 6.98 (d, 4H, Hm), 3.31 (dt, 8H, CH3CH2),
(16) Leung, W.-H.; Zheng, H.; Chim, J . L. C.; Chan, J .; Wong, W.-
T.; Williams, I. D. J . Chem. Soc., Dalton Trans. 2000, 423.
(17) Leung, W.-H.; Chim, J . L. C.; Hun, T. S. M.; Williams, I. D.;
Wong, W.-T. Inorg. Chem. 1997, 36, 4432.
(18) Dehand, J .; Rose, J . Inorg. Chim. Acta 1979, 37, 249.

4020 Organometallics, Vol. 21, No. 19, 2002
Notes
2.19 (s, 18H, Me), 2.01 (s, 6H, Me), 1.32 (t, 12H, CH3CH2). MS
(FAB): m/z 685 (M+ - Et4N + 1), 650 ([Ru(Sxylyl)4] + 1), 512
1.35 (t, 9H, CH3CH2). IR (KBr, cm-1): νCtC 2092. MS (FAB):
m/z 704 ([Os(Sxylyl)3(CtCPh)]), 567 ([Os(SR)2(CtCPh)] - 1),
462 ([Os(SR)2] + 1). Anal. Calcd for C38H47ClNS3Os‚H2O: C,
53.23; H, 5.70; N, 1.63. Found: C, 52.82; H, 5.51; N, 1.63.
P r ep a r a tion of [Ru (Sxylyl)3Cl(t-Bu NC)] (7). To a solu-
tion of 4 (100 mg, 0.145 mmol) in CH2Cl2 (20 mL) was added
1 equiv of t-BuNC (12 µL, 0.145 mmol), and the mixture was
stirred at room temperature for 2 h, during which time there
was a color change from brown to yellowish brown. The solvent
was pumped off, and the residue was washed with hexane.
Recrystallization from CH2Cl2/hexane afforded a yellow solid
(91 mg, 86%). 1H NMR (CDCl3): δ 7.35 (t, 1H, Hp), 7.21 (t,
2H, Hp), 7.12 (d, 2H, Hm), 7.01 (d, 4H, Hm), 2.27 (s, 12H, Me),
2.15 (s, 6H, Me), 1.34 (s, 9H, t-Bu). IR (KBr, cm-1): ν(NtC)
2106. MS (FAB): m/z 596 (M+ - Cl + 1), 512 (M+ - t-BuNC
+ 1), 459 ([Ru(Sxylyl)2(t-BuNC)] + 1).
([Ru(Sxylyl)3]), 373 ([Ru(Sxylyl)2] - 1). Anal. Calcd for C40H56
-
ClNS4Ru‚CH2Cl2‚H2O: C, 53.62; H, 6.54; N, 1.53. Found: C,
52.84; H, 7.21; N, 1.73.
P r ep a r a tion of [Ru (Sxylyl)3Cl(MeCN)] (3). This was
prepared according to a literature method.7d To 1 (200 mg, 0.29
mmol) in THF (25 mL) was added HCl (2.32 mL of a 1.5 M
solution in Et2O), and the mixture was stirred overnight at
room temperature. The solvent was pumped off, and the
residue was washed with hexane and Et2O. Recrystallization
from CH2Cl2/Et2O afforded a brown crystalline solid (162 mg,
96%). 1H NMR (CDCl3): δ 7.32 (t, 1H, Hp), 7.20 (t, 2H, Hp),
7.12 (d, 2H, Hm), 7.03 (d, 4H, Hm), 2.24 (s, 12H, Me), 2.11 (s,
6H, Me), 2.03 (s, 3H, MeCN). MS (FAB): m/z 589 (M+ + 1),
553 (M+ - Cl + 1), 547 (M+ - MeCN + 1), 512 ([Ru(Sxylyl)3]),
373 ([Ru(Sxylyl)2] - 1). Anal. Calcd for C26H30ClNRuS3: C,
53.00; H, 5.13; N, 2.38. Found: C, 52.24; H, 5.08; N, 2.32.
P r ep a r a tion of [Et4N][Ru (Sxylyl)3Cl(CtCP h )] (4). A
mixture of 2 (150 mg, 0.185 mmol) and phenylacetylene (94
mg, 0.92 mmol) in CH2Cl2 (30 mL) were stirred overnight at
room temperature. During this time, the solution changed from
brown to dark green. The solvent was pumped off, and the
residue was washed with hexane and Et2O. Recrystallization
from CH2Cl2/Et2O gave dark green crystals of 4 (yield 72 mg,
58%). 1H NMR (CDCl3): δ 7.31 (t, 1H, Hp), 7.21 (t, 2H, Hp),
7.12 (d, 2H, Hm), 7.05 (d, 4H, Hm), 6.67-7.00 (m, 5H, Ph), 3.34
(dt, 8H, CH3CH2), 2.32 (s, 12H, Me), 2.24 (s, 6H, Me), 1.31 (t,
12H, CH3CH2). IR (KBr, cm-1): νCtC 2052. MS (FAB): m/z 650
(M+ - Et4N), 614 ([Ru(Sxylyl)3(CtCPh)]), 476 ([Ru(Sxylyl)2(Ct
P r ep a r a tion of tr a n s-[Ru (t-Bu NC)4(Sxylyl)2] (8). To a
solution of 4 (100 mg, 0.145 mmol) in CH2Cl2 (20 mL) was
added 4 equiv of t-BuNC (48 µL, 0.58 mmol). The mixture was
stirred at room temperature for 30 min and gradually turned
yellow. After removal of the solvent under vacuum, the residue
was extracted with hexane. Concentration and cooling at -20
1
°C afforded yellow crystals (61 mg, 56%). H NMR (CDCl3): δ
6.76 (t, 2H, Hp), 6.90 (d, 4H, Hm), 2.58 (s, 12H, Me), 1.33 (s,
36H, t-Bu). IR (KBr, cm-1): 2074 ν(NtC). MS (FAB): m/z 708
(M+ + 1), 625 (M+ - t-BuNC + 1), 571 (M+ - Sxylyl + 1).
Anal. Calcd for C36H54N4RuS2: C, 61.07; H, 7.69; N, 7.91.
Found: C, 59.84; H, 7.36; N, 7.50.
X-r a y Str u ctu r e Deter m in a tion of 2‚CH2Cl2, 3, 5, a n d
8‚2H2O. The crystal data for 2‚CH2Cl2, 3, 5, and 8‚2H2O are
summarized in Table 1. The crystals were mounted on a glass
fiber using epoxy resin. Data were collected on a Bruker AXS
SMART CCD diffractometer with graphite-monochromated Mo
KR (λ ) 0.710 73 Å) radiation at room temperature. Structural
determinations were made using the SHELXTL package of
programs.19 All refinements were carried out by full-matrix
least squares using anisotropic displacement parameters for
all non-hydrogen atoms. The hydrogen atoms were generated
in their idealized positions and allowed to ride on the respec-
tive carbon atoms.
CPh)]), 373 ([Ru(Sxylyl)2] - 1). Anal. Calcd for C39H52
-
ClNRuS3: C, 61.02; H, 6.83; N, 1.82. Found: C, 60.52; H, 6.73;
N, 1.79.
P r ep a r a tion of [Et3NH][Ru (Sxylyl)3(CtCtol)] (5). To a
mixture of 3 (120 mg, 0.204 mmol) and 4-tolylacetylene (107
mg, 0.95 mmol) in CH2Cl2 (30 mL) was added Et3N (ca. 0.1
mL), and the mixture was stirred for ca. 2 h until the color of
the mixture changed from brown to dark green. The solvent
was pumped off, and the residue was recrystallized from CH2-
1
Cl2/Et2O to give dark green crystals (yield 132 mg, 85%). H
NMR (CDCl3): δ 7.30 (t, 1H, Hp), 7.21 (t, 2H, Hp), 7.12 (d, 2H,
Hm), 7.05 (d, 4H, Hm), 6.84 (d, 2H, Ho), 6.14 (d, 2H, Hm), 4.82
(s br, 1H, NH), 3.33 (dt, 8H, CH3CH2), 2.31 (s, 12H, CH3), 2.23
(s, 6H, CH3), 2.16 (s, 3H, CH3), 1.33 (t, 9H, CH3CH2). IR (KBr,
Ack n ow led gm en t. This work has been supported
by The Hong Kong University of Science and Technology
and the Areas of Excellence Scheme established under
the University Grants Committee of the Hong Kong
Special Administrative Region, People’s Republic of
China (Project No. AoE/P-10/01-1).
cm-1): νCtC 2094. MS (FAB): m/z 628 (M+ - Cl), 491 (M+
-
Cl - Sxylyl - 1). Anal. Calcd for C41H56NClS3Ru: C, 61.90;
H, 7.10; N, 1.76. Found: C, 61.13; H, 6.92; N, 1.73.
P r ep a r a tion of [Et3NH][Os(Sxylyl)3Cl(CtCP h )] (6). To
a mixture of the compound [Os(Sxylyl)3(MeCN)Cl]14 (135 mg,
0.20 mmol) and phenylacetylene (100 mg, 0.99 mmol) in CH2-
Cl2 (30 mL) was added Et3N (ca. 0.1 mL), and this mixture
was stirred at room temperature for 4 h. The solvent was
pumped off, and the residue was recrystallized from CH2Cl2/
Et2O to afford dark green crystals (84 mg, 71%). 1H NMR
(CDCl3): δ 7.36 (t, 1H, Hp), 7.22 (t, 2H, Hp), 7.14 (d, 2H, Hm),
7.05 (d, 4H, Hm), 6.63-6.98 (m, 5H, Ph), 4.82 (s br., 1H, NH),
3.34 (dt, 6H, CH3CH2), 2.36 (s, 12H, Me), 2.22 (s, 6H, Me),
Su p p or tin g In for m a tion Ava ila ble: Tables of final
atomic coordinates, anisotropic displacement parameters, and
bond lengths and angles of 2‚CH2Cl2, 3, 5, and 8‚2H2O. This
material is available free of charge via the Internet at
http://pubs.acs.org.
OM011019T
(19) Sheldrick, G. M. SHELXTL Reference Manual, version 5.1;
Siemens Energy and Automation: Madison, WI, 1997.