Tethered silyl complexes from nucleophilic substitution reactions at the Si - Cl bond of the chloro(diphenyl)silyl ligand in Ru(SiClPh2)(κ2-S2 CNMe2)(CO)(PPh3)2

Article abstract of DOI:10.1016/j.jorganchem.2004.06.031

Crystal structure determination of RuH(κ²-S₂ CNMe₂)(CO)(PPh₃)₂ (1) confirms that the triphenylphosphine ligands are arranged mutually trans. 1 reacts readily with HSiClPh₂ to eliminate H₂ and produce the six-coordinate silyl complex, Ru(SiClPh₂) (κ²-S²CNMe²)(CO)(PPh³) ² (2). Crystal structure determination of 2 reveals the same geometrical arrangement of ligands as in 1 with the silyl ligand replacing the hydride ligand. The chloride bound to silicon in 2 is replaced through reactions with 2-hydroxypyridine, 2-aminopyridine, and thallium acetate, producing, respectively, the mono-PPh³ complexes, Ru(κ²(Si,N)-SiPh²OC⁵ H⁴N)(κ²-S²CNMe²)(CO) (PPh³) (3), Ru(κ²(Si,N)-SiPh² NHC⁵H⁴N)(κ²-S² CNMe²)(CO)(PPh³) (4), and Ru(κ² (Si,O)-SiPh²OCMeO)(κ²-S² CNMe²)(CO)(PPh³) (5). Crystal structure determinations of 3, 4, and 5 confirm that in each case there is formation of a five-membered chelate ring tethering the silyl ligand to ruthenium. In the formation of 3, 4, and 5 the Si-ligand and the two S atoms of the dimethyldithiocarbamate ligand remain meridional but the remaining triphenylphosphine ligand and the carbonyl ligand are interchanged in position leaving the donor atom of the tether trans to the CO ligand. An alternative way of considering the tethered silyl ligands in 3, 4, and 5 is as tethered, base-stabilised, silylene ligands and the structural data give some support for a contribution from this bonding model.

Full text of DOI:10.1016/j.jorganchem.2004.06.031

Journal of Organometallic Chemistry 689 (2004) 2979–2987
www.elsevier.com/locate/jorganchem
Tethered silyl complexes from nucleophilic substitution reactions
at the Si–Cl bond of the chloro(diphenyl)silyl ligand in
Ru(SiClPh2)(j2-S2CNMe2)(CO)(PPh3)2
Wai-Him Kwok, Guo-Liang Lu, Clifton E.F. Rickard,
*
*
Warren R. Roper , L. James Wright
Department of Chemistry, The University of Auckland, P.O. Bag 92019, Auckland, New Zealand
Received 14 April 2004; accepted 10 June 2004
Available online 6 August 2004
Abstract
Crystal structure determination of RuH(j2-S2CNMe2)(CO)(PPh3)2 (1) confirms that the triphenylphosphine ligands are arranged
mutually trans. 1 reacts readily with HSiClPh2 to eliminate H2 and produce the six-coordinate silyl complex, Ru(SiClPh2)(j2-
S2CNMe2)(CO)(PPh3)2 (2). Crystal structure determination of 2 reveals the same geometrical arrangement of ligands as in 1 with
the silyl ligand replacing the hydride ligand. The chloride bound to silicon in 2 is replaced through reactions with 2-hydroxypyridine,
2-aminopyridine, and thallium acetate, producing, respectively, the mono-PPh3 complexes, Ru(j2(Si,N)-SiPh2OC5H4N)
(j2-S2CNMe2)(CO)(PPh3) (3), Ru(j2(Si,N)-SiPh2NHC5H4N)(j2-S2CNMe2)(CO)(PPh3) (4), and Ru(j2(Si,O)-SiPh2OCMeO)(j2-
S2CNMe2)(CO)(PPh3) (5). Crystal structure determinations of 3, 4, and 5 confirm that in each case there is formation of a five-mem-
bered chelate ring tethering the silyl ligand to ruthenium. In the formation of 3, 4, and 5 the Si-ligand and the two S atoms of the
dimethyldithiocarbamate ligand remain meridional but the remaining triphenylphosphine ligand and the carbonyl ligand are inter-
changed in position leaving the donor atom of the tether trans to the CO ligand. An alternative way of considering the tethered silyl
ligands in 3, 4, and 5 is as tethered, base-stabilised, silylene ligands and the structural data give some support for a contribution from
this bonding model.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Silyl complex; Ruthenium; X-ray crystal structure; Bidentate ligand
1. Introduction
dictable, but two trends which have emerged are that
more electron-rich metal centers reduce the reactivity
of the Si–Cl bonds [2] while coordinative unsaturation
at the metal increases the reactivity of the Si–Cl bonds
[1d]. To contribute to further understanding of the reac-
tivity of chloro-substituted silyl ligands we have devel-
oped a convenient route to a coordinatively saturated
chloro(diphenyl)silyl complex of ruthenium(II) and ex-
amined some features of its chemistry.
Metal complexes containing chloro-substituted silyl
ligands, LnM–SiR3 ꢀ nCln (n=1–3), have proved to be
useful substrates, through nucleophilic substitution re-
actions at the Si–Cl bonds, for the synthesis of a wide
range of silyl complexes with interestingly functionalised
silyl ligands [1]. The reactivity of the Si–Cl bonds in all
chlorosilyl ligands is variable, and not particularly pre-
Herein, we report (i) the synthesis of Ru(SiClPh2)(j2-
S2CNMe2)(CO)(PPh3)2 (2) from RuH(j2-S2CNMe2)-
(CO)(PPh3)2 (1) and HSiClPh2, (ii) the reactions of the
Si–Cl bond in 2 with 2-hydroxypyridine, 2-aminopyri-
dine, or thallium acetate which lead to the tethered silyl
*
Corresponding authors. Tel.: +64-9-373-7999x8320; fax: +64-9-
373-7422.
E-mail address: w.roper@auckland.ac.nz (W.R. Roper).
0022-328X/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.06.031

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W.-H. Kwok et al. / Journal of Organometallic Chemistry 689 (2004) 2979–2987
complexes, Ru(j2(Si,N)-SiPh2OC5H4N)(j2-S2CNMe2)-
(CO)(PPh3) (3), Ru(j2(Si,N)-SiPh2NHC5H4N)(j2-S2-
CNMe2)(CO)(PPh3) (4), or Ru(j2(Si,O)-SiPh2OCMeO)-
(j2-S2CNMe2)(CO)(PPh3) (5), respectively, and (iii) the
crystal structure determinations of complexes 1–5.
For 1 and 2, the molecular structures are shown in
Figs. 1 and 2, and selected bond lengths and angles
are given in Tables 2 and 3, respectively. The geometry
of both complexes is octahedral with the two triphenyl-
phosphine ligands arranged mutually trans. The Ru–H
˚
distance in 1 is 1.718(18) A and this can be compared
˚
with the average (1.581 with SD 0.119 A) of 360 meas-
2. Results and discussion
ured distances recorded in the Cambridge Crystallo-
graphic Data Base. The attachment of the bidentate
dimethyldithiocarbamate ligand is unsymmetrical for
both 1 and 2 with the Ru–S distances greater when S
is trans to the hydride ligand in 1 and to the silyl ligand
in 2. The Ru–S distances trans to CO are almost iden-
2.1. Synthesis of Ru(SiClPh2)(j2-S2CNMe2)(CO)-
(PPh3)2 (2) from RuH(j2-S2CNMe2)(CO)(PPh3)2
(1) and the structures of (1) and (2)
As depicted in Scheme 1, reaction between RuH(j2-
S2CNMe2)(CO)(PPh3)2 (1) and
tical (Ru–S, 2.4568(10) A for 1 and 2.4598(7) A for 2).
Based on the Ru–S distances the trans influence of the
silyl ligand is slightly greater than the hydride ligand in
˚
˚
a
10-fold excess
HSiClPh2, leads to pale yellow Ru(SiClPh2)(j2-
S2CNMe2)(CO)(PPh3)2 (2) in high yield. The IR spec-
trum of 2 shows a m(CO) band at 1915 cmꢀ1 which is
slightly lower than the value of 1920 cmꢀ1 reported
for 1 [3]. In the 1H NMR spectrum two resonances
are seen for the inequivalent methyl groups of the dith-
iocarbamate ligand at 2.16 and 2.35 ppm. This is con-
sistent with the structure shown in Scheme 1 which
has been confirmed by crystal structure determination
(see below). The geometry of 2 is therefore the same
as 1 with the silyl ligand replacing the hydride ligand.
For the purpose of a close structural comparison of
all the Ru-ligand bond distances in these two com-
pounds the structures of both 1 and 2 were determined.
Crystal data and refinement details for 1, 2, and all other
structures reported in this paper, are given in Table 1.
˚
these complexes (Ru–S, 2.4884(9) A for 1 and 2.4980(7)
˚
A for 2). The Ru–P distances in 1 (2.3328(9) and
˚
2.3784(9) A) are considerably less than the Ru–P dis-
˚
tances in 2 (2.3985(7) and 2.4112(7) A), presumably re-
flecting the lesser steric demands of the hydride ligand
compared to the silyl ligand. The Ru–Si distance in 2
˚
is 2.4089(7) A, which is very close to the average
˚
(2.4035 with SD 0.0478 A) of 44 measured distances re-
corded in the Cambridge Crystallographic Data Base
for octahedral ruthenium silyl complexes where silicon
˚
is four-coordinate. The Si–Cl distance is 2.1518(10) A,
which is remarkably long when compared with the av-
˚
erage of recorded Si–Cl distances of 2.0579 A, SD
˚
0.0435 A (Cambridge Crystallographic Data Base). An-
other unusual feature associated with the Si–Cl bond is
that the angle Ru–Si–Cl is less than tetrahedral
(107.87(4)ꢁ) whereas the Ru–Si–phenyl angles are
119.18 and 124.51ꢁ. This less-than-tetrahedral angle
for Ru–Si–Cl and much greater-than-tetrahedral angles
for Ru–Si–phenyl, has the effect of ‘‘flattening’’ the ar-
rangement of Ru and the two phenyl substituents on Si
(sum of angles 345.23ꢁ). This effect is even more accen-
tuated in the structures 3, 4, and 5 discussed below.
Other chloro(diphenyl)silyl complexes all have M–Si–
Cl angles greater than tetrahedral [4] except for CpFe
(CO)2SiPh(C6H4OMe-2)Cl where the angle Fe–Si–Cl
is 108.09(3)ꢁ [1h].
2.2. Nucleophilic substitution at the Si–Cl bond of 2 by 2-
hydroxypyridine, 2-aminopyridine, and acetate, to give
the corresponding tethered silyl complexes Ru(j2(Si,N)-
SiPh2OC5H4N)(j2-S2CNMe2)(CO)(PPh3) (3), Ru(j2-
(Si,N)-SiPh2NHC5H4N)(j2-S2CNMe2)(CO)(PPh3)
(4), and Ru(j2(Si,O)-SiPh2OCMeO)(j2-S2CNMe2)-
(CO)(PPh3) (5)
As shown in Scheme 1 complex 2 reacts readily with
2-hydroxypyridine, 2-aminopyridine, and thallium ace-
tate to give, in good yield, the colourless, tethered, silyl
complexes Ru(j2(Si,N)-SiPh2OC5H4N)(j2-S2CNMe2)-
Scheme 1. Synthesis and reactions of the chloro(diphenyl)silyl com-
plex, Ru(SiClPh2)(j2-S2CNMe2)(CO)(PPh3)2 (2).

Table 1
Data collection and processing parameters for 1–5
1
2
3Æ2.5C6H6
4
5ÆCH2Cl2
Formula
C40H37NOP2RuS2
774.84
C52H46ClNOP2RuS2Si
991.57
C54H50N2O2PRuS2Si
983.21
Triclinic
C39H36N3OPRuS2Si
786.96
C37H36Cl2NO3PRuS2Si
837.82
Molecular weight
Crystal system
Space group
Monoclinic
P21/c
Monoclinic
P21/c
Monoclinic
P21/c
Monoclinic
C2/c
ꢀ
P1
˚
a (A)
13.4658(2)
15.4931(2)
18.5896(2)
90.0
10.2887(1)
21.8567(3)
20.7550(2)
90.0
11.7848(1)
12.1648(1)
19.3655(1)
107.160(1)
94.832(1)
10.6009(1)
17.8163(1)
19.3417(1)
90.0
40.9807(4)
10.1942(1)
23.1315(4)
90.0
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
110.048(1)
90.0
93.151(1)
90.0
97.622(1)
90.0
121.310(1)
90.0
111.388(1)
2411.86
3
˚
V (A )
3643.29(8)
4
1.413
4660.27(9)
4
1.413
3620.77(4)
4
1.444
8256.39(18)
8
1.348
Z
2
1.354
d(calc) (gcmꢀ3
F(000)
)
1592
0.66
2040
0.62
1018
0.51
1616
0.66
3424
0.71
l (mmꢀ1
)
Crystal size (mm)
2h (min–max) (ꢁ)
Reflections collected
Independent reflections
A (min–max)
Goodness-of-fit on F2
R (observed data)
R (all data)
0.44·0.18·0.14
1.6–27.5
20,768
0.45·0.36·0.18
1.4–27.4
26,184
0.43·0.33·0.21
1.8–27.5
23,323
0.38·0.28·0.21
1.5–27.5
21,981
0.38·0.08·0.07
1.7–25.0
23,124
7952Rint =0.0349
0.758–0.913
1.081
10,138Rint =0.0265
0.768–0.897
1.074
10,357Rint =0.0158
0.809–0.900
1.018
8002Rint =0.0217
0.787–0.874
1.102
8068Rint =0.0674
0.774–0.952
1.001
R1 =0.0461, wR2 =0.0956
R1 =0.0694, wR2 =0.1058
1.14–1.00
R1 =0.0363, wR2 =0.0706
R1 =0.0523, wR2 =0.0773
0.44–0.40
R1 =0.0257, wR2 =0.0639
R1 =0.0304, wR2 =0.0667
0.61–0.49
R1 =0.0364, wR2 =0.0872
R1 =0.0471, wR2 =0.0944
0.63–0.46
R1 =0.0576, wR2 =0.1396
R1 =0.0880, wR2 =0.1535
2.22–1.08
ꢀ3
˚
Diff. map (min–max) (eA
)
P
P
P
P
2
2
1=2
R ¼
jj F o j ꢀ j F c jj = j F o j; wR2 ¼ f ½wðF 2o ꢀ F c2Þ ꢁ= ½wðF o2Þ ꢁg
.

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W.-H. Kwok et al. / Journal of Organometallic Chemistry 689 (2004) 2979–2987
Table 2
˚
Selected bond lengths (A) and angles (ꢁ) for 1
Bond lengths
Ru–C(1)
Ru–P(2)
Ru–P(1)
Ru–S(1)
Ru–S(2)
Ru–H(1)
S(1)–C(2)
S(2)–C(2)
N–C(2)
1.859(5)
2.3328(9)
2.3784(9)
2.4568(10)
2.4884(9)
1.718(18)
1.716(4)
1.714(4)
1.333(4)
1.463(5)
1.465(5)
N–C(4)
N–C(3)
Bond angles
C(1)–Ru–P(2)
C(1)–Ru–P(1)
P(2)–Ru–P(1)
C(1)–Ru–S(1)
P(2)–Ru–S(1)
P(1)–Ru–S(1)
85.95(13)
89.77(13)
175.68(3)
178.19(13)
95.55(3)
88.72(3)
107.74(14)
91.27(3)
89.48(3)
71.25(3)
94.3(12)
83.8(11)
97.1(11)
86.9(12)
157.1(12)
Fig. 1. Molecular geometry of RuH(j2-S2CNMe2)(CO)(PPh3)2 (1).
C(1)–Ru–S(2)
P(2)–Ru–S(2)
P(1)–Ru–S(2)
S(1)–Ru–S(2)
C(1)–Ru–H(1)
P(2)–Ru–H(1)
P(1)–Ru–H(1)
S(1)–Ru–H(1)
S(2)–Ru–H(1)
NH function. In the 13C NMR spectra of 4 and 5 a dou-
blet signals for the CO ligands are seen at 204.9 ppm
(2JCP =16.1 Hz) and at 204.7 ppm (2JCP =16.1 Hz), re-
spectively. For 3 the CO signal was seen at 204.6 ppm
but the coupling to phosphorus was not resolved.
2.3. Structure determinations of the tethered silyl com-
plexes 3, 4, and 5
Fig. 2. Molecular geometry of Ru(SiClPh2)(j2-S2CNMe2)(CO)(PPh3)2
(2).
The molecular geometries of the complexes 3, 4, and
5 are shown in Figs 3–5, respectively. Selected bond
lengths and angles are presented in Tables 4–6. The ge-
ometry of all three complexes is octahedral. The attach-
ment of the bidentate dimethyldithiocarbamate ligand is
again unsymmetrical for all three compounds with the
Ru–S distances greater when S is trans to the silyl ligand
(CO)(PPh3) (3), Ru(j2(Si,N)-SiPh2NHC5H4N)(j2-S2-
CNMe2)(CO)(PPh3) (4), and Ru(j2(Si,O)-SiPh2OCMe-
O)(j2-S2CNMe2)(CO)(PPh3) (5), respectively. In each
reaction a triphenylphosphine ligand is lost and there
is a rearrangement of the coordination sphere in that
the remaining triphenylphosphine ligand, which was
originally in a facial configuration with the two sulfur
atoms of the chelating dimethyldithiocarbamate ligand,
is now found in a meridional configuration with the two
S atoms. At the same time the CO ligand moves from a
meridional arrangement with respect to the two S atoms
to one in which this arrangement becomes facial. The IR
spectra of 3, 4, and 5 show m(CO) bands at 1915, 1925,
˚
(3, 2.5296(4); 4, 2.5189(7); 5, 2.4940(13) A). The smaller
Ru–S distances trans to PPh3 are (3, 2.4529(4); 4,
˚
2.4374(7); 5, 2.4249(12) A). The Ru–Si distances for 3
˚
˚
˚
(2.3487(4) A), 4 (2.3400(7) A), and 5 (2.3499(13) A)
are all considerably shortened with respect to the parent
˚
complex 2 (2.4089(7) A). This can probably be attributed
mainly to the formation of the favourable five-mem-
bered chelate ring but some contribution from possible
silylene character in this bond should not be ignored.
This is also suggested by the ‘‘flattening’’ of the two phe-
nyl substituents and the bond to Ru, about Si. The sum
1
and 1909 cmꢀ1, respectively. The H NMR spectrum
of 4 shows a resonance at 5.15 ppm assigned to the

W.-H. Kwok et al. / Journal of Organometallic Chemistry 689 (2004) 2979–2987
2983
Table 3
˚
Selected bond lengths (A) and angles (ꢁ) for 2
Bond lengths
Ru–C(1)
Ru–P(1)
Ru–Si
1.845(2)
2.3985(7)
2.4089(7)
2.4112(7)
2.4598(7)
2.4980(7)
2.1518(10)
1.910(3)
1.914(3)
1.714(3)
1.725(3)
1.326(3)
1.461(4)
1.468(4)
1.159(3)
Ru–P(2)
Ru–S(1)
Ru–S(2)
Cl–Si
Si–C(81)
Si–C(71)
S(1)–C(2)
S(2)–C(2)
N(1)–C(2)
N(1)–C(4)
N(1)–C(3)
O(1)–C(1)
Bond angles
C(1)–Ru–P(1)
C(1)–Ru–Si
P(1)–Ru–Si
Fig. 4. Molecular geometry of Ru(j2(Si,N)-SiPh2NHC5H4N)(j2-
S2CNMe2)(CO)(PPh3) (4) (only one enantiomer is shown).
88.14(8)
92.53(8)
99.65(2)
89.55(8)
163.94(2)
96.33(2)
179.39(8)
91.97(2)
88.04(2)
90.17(2)
108.31(8)
82.50(2)
159.14(2)
83.15(2)
71.12(2)
101.54(12)
97.68(9)
101.64(9)
119.18(9)
124.51(8)
107.87(4)
C(1)–Ru–P(2)
P(1)–Ru–P(2)
Si–Ru–P(2)
C(1)–Ru–S(1)
P(1)–Ru–S(1)
Si–Ru–S(1)
P(2)–Ru–S(1)
C(1)–Ru–S(2)
P(1)–Ru–S(2)
Si–Ru–S(2)
P(2)–Ru–S(2)
S(1)–Ru–S(2)
C(81)–Si–C(71)
C(81)–Si–Cl
C(71)–Si–Cl
C(81)–Si–Ru
C(71)–Si–Ru
Cl–Si–Ru
Fig. 5. Molecular geometry of Ru(j2(Si,O)-SiPh2OCMeO)(j2-
S2CNMe2)(CO)(PPh3) (5) (only one enantiomer is shown).
of the angles Ru–Si–phenyl, Ru–Si–phenyl, and phenyl–
Si–phenyl is ca. 347ꢁ for 3, 346ꢁ for 4, 351ꢁ for 5. In
addition the measured Si–O and Si–N distances are
exceptionally long. The average of all reported Si–O dis-
˚
tances for four-coordinate Si is 1.6295 (SD 0.0334) A
(Cambridge Crystallographic Data Base), but the Si–O
˚
distance for 3 is 1.7333(13) A and for 5 is 1.775(3) A.
˚
Likewise, the average of all reported Si–N distances
˚
for four-coordinate Si is 1.7363 (SD 0.0378) A (Cam-
bridge Crystallographic Data Base), but the Si–N dis-
˚
tance for 4 is 1.776(2) A. The data above suggest that
the base-stabilised silylene structure (A) shown in
Scheme 2 could be a contributor to the bonding in com-
plex 5. Similar valence bond representations could be
written for complexes 3 and 4. The C–O distances within
the acetate group suggest that there is more double bond
Fig. 3. Molecular geometry of Ru(j2(Si,N)-SiPh2OC5H4N)(j2-
S2CNMe2)(CO)(PPh3) (3) (only one enantiomer is shown).

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W.-H. Kwok et al. / Journal of Organometallic Chemistry 689 (2004) 2979–2987
Table 4
Table 5
˚
˚
Selected bond lengths (A) and angles (ꢁ) for 3
Selected bond lengths (A) and angles (ꢁ) for 4
Bond lengths
Ru–C(1)
Ru–N(2)
Ru–P
Bond lengths
Ru–C(1)
Ru–N(3)
Ru–P
1.8269(17)
2.2167(14)
2.3409(4)
2.3487(4)
2.4529(4)
2.5296(4)
1.7333(13)
1.8857(18)
1.8946(18)
1.7271(17)
1.7209(17)
1.159(2)
1.827(3)
2.190(2)
2.3263(7)
2.3400(7)
2.4374(7)
2.5189(7)
1.776(2)
1.889(3)
1.899(3)
1.714(3)
1.718(3)
1.148(4)
1.326(3)
Ru–Si
Ru–Si
Ru–S(1)
Ru–S(2)
Si–O(2)
Ru–S(1)
Ru–S(2)
Si–N(2)
Si–C(11)
Si–C(21)
S(1)–C(2)
S(2)–C(2)
O(1)–C(1)
O(2)–C(5)
N(1)–C(2)
N(1)–C(4)
N(1)–C(3)
Si–C(11)
Si–C(21)
S(1)–C(2)
S(2)–C(2)
O–C(1)
1.337(2)
1.328(2)
N(1)–C(2)
1.462(2)
1.465(2)
Bond angles
C(1)–Ru–N(3)
C(1)–Ru–P
173.10(10)
91.32(9)
92.29(6)
92.10(9)
81.52(6)
99.04(2)
90.71(9)
86.68(6)
170.66(2)
90.00(2)
94.00(9)
91.19(6)
99.68(2)
160.15(3)
71.08(2)
107.28(12)
102.37(12)
104.07(12)
98.50(8)
112.97(8)
129.23(9)
Bond angles
C(1)–Ru–N(2)
C(1)–Ru–P
N(3)–Ru–P
C(1)–Ru–Si
N(3)–Ru–Si
P–Ru–Si
170.81(6)
92.44(5)
92.15(4)
93.98(5)
N(2)–Ru–P
C(1)–Ru–Si
N(2)–Ru–Si
P–u–Si
C(1)–Ru–S(1)
N(3)–Ru–S(1)
P–Ru–S(1)
77.60(4)
96.251(16)
90.46(5)
86.55(4)
C(1)–Ru–S(1)
N(2)–Ru–S(1)
P–Ru–S(1)
Si–Ru–S(1)
C(1)–Ru–S(2)
N(3)–Ru–S(2)
P–Ru–S(2)
168.920(15)
94.214(15)
94.20(5)
Si–Ru–S(1)
C(1)–Ru–S(2)
N(2)–Ru–S(2)
P–Ru–S(2)
Si–Ru–S(2)
93.02(4)
S(1)–Ru–S(2)
N(2)–Si–C(11)
N(2)–Si–C(21)
C(11)–Si–C(21)
N(2)–Si–Ru
C(11)–Si–Ru
C(21)–Si–Ru
98.313(14)
162.959(16)
70.796(14)
102.12(7)
103.54(7)
103.22(8)
101.00(4)
126.97(5)
116.60(6)
Si–Ru–S(2)
S(1)–Ru–S(2)
O(2)–Si–C(11)
O(2)–Si–C(21)
C(11)–Si–C(21)
O(2)–Si–Ru
C(11)–Si–Ru
C(21)–Si–Ru
Ph2OC5H4N)(j2-S2CNMe2)(CO)(PPh3) (3), Ru(j2-
(Si,N)-SiPh2NHC5H4N)(j2-S2CNMe2)(CO)(PPh3) (4),
and
Ru(j2(Si,O)-SiPh2OCMeO)(j2-S2CNMe2)(CO)-
˚
character in the C–O(bound to Ru) bond (1.239(5) A)
than there is in the C–O (bound to Si) bond (1.297(5)
˚
A). This is consistent with valence bond structure B be-
(PPh3) (5) reveal a bonding situation within the five-
membered rings which is intermediate between ‘‘tethered
silyl’’ (predominant) and ‘‘base-stabilised silylene’’.
ing more important than valence bond structure A (see
Scheme 2). Thus a description of the chelate ligand as
a tethered silyl ligand seems more appropriate than as
a base-stabilised silylene ligand.
4. Experimental
4.1. General procedures and instruments
3. Conclusions
Standard laboratory procedures were followed as
have been described previously [5]. The compound
RuH(j2-S2CNMe2)(CO)(PPh3)2 [3], was prepared by
the literature method.
It has been demonstrated that the Si–Cl bond in the
Ru(SiClPh2)(j2-
six-coordinate
silyl
complex,
S2CNMe2)(CO)(PPh3)2 (2) is reactive towards the three
reagents, 2-hydroxypyridine, 2-aminopyridine, and thal-
lium acetate, producing in each case mono-triphenyl-
phosphine complexes containing tethered silyl ligands.
Crystal structure determinations of Ru(j2(Si,N)-Si-
Infrared spectra (4000–400 cmꢀ1) were recorded as
Nujol mulls between KBr plates on a Perkin–Elmer Par-
agon 1000 spectrometer. NMR spectra were obtained on
either a Bruker DRX 400 or Bruker AC 200 at 25ꢁC.
1
For the Bruker DRX 400, H and 13C NMR spectra

W.-H. Kwok et al. / Journal of Organometallic Chemistry 689 (2004) 2979–2987
2985
(1H) and 50.3 (13C) MHz, respectively. Resonances are
quoted in ppm and 1H NMR spectra referenced to either
tetramethylsilane (0.00 ppm) or the proteo-impurity in
the solvent (7.25 ppm for CHCl3). 13C NMR spectra
were referenced to CDCl3 (77.00 ppm). Elemental anal-
yses were obtained from the Microanalytical Laboratory,
University of Otago.
Table 6
˚
Selected bond lengths (A) and angles (ꢁ) for 5
Bond lengths
Ru–C(1)
Ru–O(2)
Ru–P
1.801(5)
2.182(3)
2.3386(12)
2.3499(13)
2.4249(12)
2.4940(13)
1.775(3)
1.881(5)
1.888(5)
1.734(5)
1.707(5)
1.338(6)
1.441(8)
1.504(8)
1.176(5)
1.239(5)
1.297(5)
1.508(6)
Ru–Si
Ru–S(1)
Ru–S(2)
Si–O(3)
4.2. Preparation of Ru(SiClPh2)(j2-S2CNMe2)-
(CO)(PPh3)2 (2)
Si–C(21)
Si–C(11)
S(1)–C(4)
S(2)–C(4)
N–C(4)
HSiPh2Cl (2.53 ml, 12.9 mmol) was added to a col-
ourless solution of RuH(j2-S2CNMe2)(CO)(PPh3)2
(1.00 g, 1.29 mmol) in toluene under nitrogen. The reac-
tion mixture was heated to 85ꢁC for 1.5 h. The resulting
pale orange suspension was concentrated to approx. 2
ml and hexane was added to give pure 2 as a pale yellow
solid which was collected and washed with hexane (1.20
g, 94%). Anal. Calc. for C52H46ClNOP2RuS2Si: C,
62.99; H, 4.68; N, 1.41. Found: C, 62.78; H, 4.71; N,
N–C(5)
N–C(6)
O(1)–C(1)
O(2)–C(2)
O(3)–C(2)
C(2)–C(3)
Bond angles
C(1)–Ru–O(2)
C(1)–Ru–P
172.3(2)
1
1.43%. IR (cmꢀ1): 1915s m(CO). H NMR (CDCl3, d):
90.69(15)
94.69(9)
94.44(15)
79.09(9)
100.94(5)
91.75(15)
84.00(9)
169.09(5)
89.47(5)
101.39(15)
83.48(9)
97.25(4)
155.67(5)
71.85(4)
102.8(2)
99.4(2)
2.16 (s, 3H, NMe2), 2.35 (s, 3H, NMe2), 6.99–7.58 (m,
40H, SiPh2 and PPh3). 13C NMR (CDCl3, d): 38.1
O(2)–Ru–P
C(1)–Ru–Si
2,4
(NMe2), 127.6 (t0 [5],
(SiPh2), 128.7 (SiPh2), 129.6 (s, p-C6H5), 132.9 (m, i-
J
=9.0 Hz, o-C6H5), 128.2
CP
O(2)–Ru–Si
P–Ru–Si
C(1)–Ru–S(1)
O(2)–Ru–S(1)
P–Ru–S(1)
3,5
C6H5), 134.4 (t0,
CO), 210.3 (S2CNMe2) (some coupling constants were
not resolved).
J
=10.0 Hz, m-C6H5), 178.1 (m,
CP
Si–Ru–S(1)
C(1)–Ru–S(2)
O(2)–Ru–S(2)
P–Ru–S(2)
4.3. Preparation of Ru(j2(Si,N)-SiPh2OC5H4N)(j2-
S2CNMe2)(CO)(PPh3) (3)
Si–Ru–S(2)
S(1)–Ru–S(2)
O(3)–Si–C(21)
O(3)–Si–C(11)
C(21)–Si–C(11)
O(3)–Si–Ru
Ru(SiPh2Cl)(j2-S2CNMe2)(CO)(PPh3)2 (173.5 mg,
0.175 mmol) and 2-hydroxypyridine (33.3 mg, 0.35
mmol) were added to benzene (20 ml) under nitrogen.
The white suspension was stirred for 1 h and then fil-
tered through Celite. The filtrate was concentrated and
hexane added to give a white solid. The crude product
was dissolved in CH2Cl2 and purified by chromatogra-
phy on silica gel using CH2Cl2/hexane (v/v=1:1) as elu-
ent. A white solid was obtained from the second
colourless fraction, which was recrystallised from
CH2Cl2 and heptane to give pure 3 as colourless crystals
(77 mg, 56%). Anal. Calc. for C39H35N2O2PRuS2Si: C,
58.82; H, 4.55; N, 3.61. Found: C, 58.58; H, 4.38; N,
102.8(2)
98.59(11)
118.5(2)
129.48(15)
87.7(2)
C(21)–Si–Ru
C(11)–Si–Ru
C(4)–S(1)–Ru
C(4)–S(2)–Ru
O(2)–C(2)–O(3)
O(2)–C(2)–C(3)
O(3)–C(2)–C(3)
S(2)–C(4)–S(1)
86.1(2)
123.9(4)
119.7(4)
116.3(4)
114.0(3)
were obtained operating at 400.1 (1H) and 100.6 (13C)
MHz, respectively. For the Bruker AC 200, 1H and
13C NMR spectra were obtained operating at 200.0
1
3.43%. IR (cmꢀ1): 1915 m(CO). H NMR (CDCl3, d):
3.03 (s, 3H, NMe2), 3.24 (s, 3H, NMe2), 6.31–6.34 (m,
1H, OC5H4N), 6.89–7.45 (m, 25H, SiPh2 and PPh3),
7.72 (apparent dd, 2H, J=1.1 Hz, 7.8 Hz, OC5H4N),
8.07 (apparent dd, 2H, J=1.8, 5.8 Hz, OC5H4N). 13C
NMR (CDCl3, d): 38.6 (NMe2), 39.1 (NMe2), 112.2
(OC5H4N), 115.6 (OC5H4N), 126.8 (SiPh2), 126.9
2
(SiPh2), 127.5 (SiPh2), 127.7 (d, JCP =9.1 Hz, o-
C6H5P), 129.0 (p-C6H5P), 132.8 (SiPh2), 133.0 (SiPh2),
3
133.1 (d, JCP =10.1 Hz, m-C6H5P), 134.5 (d,
1JCP =42.3 Hz, i-C6H5P), 139.1 (OC5H4N), 143.6
Scheme 2. Possible valence bond structures for Ru(j2(Si,O)-SiPh2OC-
MeO)(j2-S2CNMe2)(CO)(PPh3) (5).

2986
W.-H. Kwok et al. / Journal of Organometallic Chemistry 689 (2004) 2979–2987
(SiPh2), 143.9 (SiPh2), 148.4 (OC5H4N), 167.1
(OC5H4N), 204.6 (CO), 212.5 (S2CNMe2). Coupling
constant for CO not resolved.
NMR (CDCl3, d): 21.4 (O2CCH3), 38.5 (NMe2), 39.0
(NMe2), 127.1 (SiPh2), 127.4 (SiPh2), 127.7 (d,
2JCP =10.1 Hz, m-C6H5P), 128.4 (SiPh2), 128.9 (SiPh2),
129.4 (s, p-C6H5P), 133.3 (SiPh2), 133.8 (d, JCP =11.1
Hz, m-C6H5P), 133.9 (SiPh2), 141.0 (SiPh2), 144.2
2
(SiPh2), 182.4 (O2CCH3), 204.7 (d, JCP =16.1 Hz,
CO), 213.1 (S2CNMe2).
3
4.4. Preparation of Ru(j2(Si,N)-SiPh2NHC5H4N)(j2-
S2CNMe2)(CO)(PPh3) (4)
Ru(SiPh2Cl)(j2-S2CNMe2)(CO)(PPh3)2 (198 mg,
0.20 mmol) and 2-aminopyridine (39 mg, 0.42 mmol)
were added to benzene (20 ml) under nitrogen. The or-
ange mixture turned to a yellow suspension and after
stirring for 16 h it was filtered through Celite. The yel-
low filtrate was evaporated to low volume and hexane
added to give pale yellow solid. This was dissolved in
CH2Cl2 and subjected to thin-layer chromatography
on silica gel using CH2Cl2/hexane (v/v=1:1) as eluent.
From the second colourless band was obtained an off-
white solid, which was recrystallised from CH2Cl2 and
heptane to give pure 4 as colourless crystals (78 mg,
50%). Anal. Calc. for C39H36N3OPRuS2SiÆ1/4CH2Cl2:
C, 58.85; H, 4.68; N, 5.28. Found: C, 58.59; H, 4.60;
4.6. X-ray crystal structure determinations for complexes
1–5
X-ray data collection was by Siemens SMART dif-
fractometer with a CCD area detector at 150 K using
graphite
monochromated
˚
Mo
Ka
radiation
(k=0.71073 A). Data were integrated and corrected
for Lorentz and polarisation effects using SAINT [6]
software. Semi-empirical absorption corrections were
applied based on equivalent reflections using SADABS
[7]. The structures were solved by Patterson and Fourier
methods and refined by full-matrix least squares on F2
using programs SHELXS [8] and SHELXL [9]. All non-
hydrogen atoms were refined anisotropically. Hydrogen
atoms were located geometrically and refined using a
riding model with thermal parameter 20% greater than
Uiso of the carrier atom. The benzene molecules of solva-
tion in 3 were ordered. The final electron density map
for 5 revealed one ordered dichloromethane of solvation
and in addition, contained numerous electron density
peaks clustered in one region of the unit cell, which
could not be resolved sensibly into a molecule and pre-
sumably represent additional disordered dichlorometh-
ane of solvation. This density was removed using the
‘‘squeeze’’ function of PLATON [10] before the final re-
finement. Crystal data and refinement details are given
in Table 1.
1
N, 5.24%. IR (cmꢀ1): 1925vs m(CO). H NMR (CDCl3,
d): 3.02 (s, 3H, NMe2), 3.21 (s, 3H, NMe2), 5.15 (s, 1H,
NHpy), 6.07 (apparent dt, 1H, J=1.1, 6.5 Hz, C5H4N),
6.60 (apparent d, 1H, J=8.2 Hz, C5H4N), 6.87–6.90 (m,
2H, SiPh2), 6.95–6.98 (m, 1H, C5H4N), 7.07–7.37 (m,
21H, SiPh2 and PPh3), 7.72 (apparent dd, 2H, J=1.3,
8.0 Hz, SiPh2), 8.11 (apparent dd, 1H, J=1.6, 6.0 Hz,
C5H4N). 13C NMR (CDCl3, d): 38.5 (NMe2), 39.1
(NMe2), 110.6 (C5H4N), 111.8 (C5H4N), 127.0 (SiPh2),
127.1 (SiPh2), 127.1 (SiPh2), 127.2 (SiPh2), 127.6 (d,
2JCP =9.1 Hz, o-C6H5P), 128.9 (p-C6H5P), 133.3 (d,
3JCP =10.1 Hz, m-C6H5P), 133.7 (SiPh2), 133.8 (SiPh2),
1
134.7 (d, JCP =42.3 Hz, i-C6H5P), 137.1 (C5H4N),
143.9 (SiPh2), 144.9 (SiPh2), 149.4 (C5H4N), 165.1
2
(C5H4N), 204.9 (d, JCP =16.1 Hz, CO), 212.5
(S2CNMe2).
5. Supplementary material
4.5. Preparation of Ru(j2(Si,O)-SiPh2OCMeO)(j2-
S2CNMe2)(CO)(PPh3) (5)
Crystallographic data (excluding structure factors)
for the structures reported have been deposited with
the Cambridge Crystallographic Data Centre as Supple-
mentary Publication Nos. 234040–234044 for 1–5, re-
spectively. Copies of this information can be obtained
free of charge from the Director, CCDC, 12 Union
Road, Cambridge, CB2 1EZ, UK (fax: +44-1223-336-
033; e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).
Ru(SiPh2Cl)(j2-S2CNMe2)(CO)(PPh3)2 (235 mg,
0.24 mmol) and thallium acetate (140 mg, 0.48 mmol)
were added to CH2Cl2 (20 ml). The orange mixture
turned to a white suspension upon stirring. This was
stirred for 2 h and then filtered through Celite. The col-
ourless filtrate was evaporated to a low volume and hex-
ane was added to give a white solid. This was
recrystallised from CH2Cl2/hexane to give pure 5 as col-
ourless crystals (128 mg, 68%). Anal. Calc. for
C36H34NO3PRuS2Si1.5CH2Cl2: C, 52.10; H, 4.15; N,
1.56. Found: C, 52.05; H, 4.34; N, 1.69. IR (cmꢀ1):
Acknowledgement
1
1909 vs m(CO); 1604 (O2CMe). H NMR (CDCl3, d):
1.97 (s, 3H, O2CCH3), 3.13 (s, 3H, NMe2), 3.21 (s,
3H, NMe2), 6.95–7.01 (m, 5H, SiPh2), 7.23–7.38 (m,
17H, SiPh2 and PPh3), 7.72–7.76 (m, 3H, SiPh2). 13C
We thank the Marsden Fund administered by the
Royal Society of NZ for supporting this work. We
also thank the Croucher Foundation, Hong Kong, for

W.-H. Kwok et al. / Journal of Organometallic Chemistry 689 (2004) 2979–2987
2987
From Molecules to Materials, VCH, Weinheim, Germany, 1996,
p. 575.
support and for granting a Postdoctoral Fellowship to
H-WK. We also thank the University of Auckland Re-
search Committee for partial support of this work
through grants-in-aid.
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