Effect of substituents on the formation of vinylideneruthenium(II) complexes. X-ray structures of RuCl2{=C=C(Z)Ph}(dcpmp) (Z = H, SiMe3; dcpmp = C5H3N(CH2PCy2)2)

Article abstract of DOI:10.1021/om020238r

Kinetic studies have been carried out for the formation of vinylideneruthenium(II) complexes RuCl₂{=C=C(Z)R}(dcpmp) [Z = H, R =p-MeOC₆H₄ (2a),p-MeC₆H₄ (2b), Ph (2c), p-BrC₆H₄ (2d

Full text of DOI:10.1021/om020238r

Organometallics 2002, 21, 3285-3291
3285
Effect of Su bstitu en ts on th e F or m a tion of
Vin ylid en er u th en iu m (II) Com p lexes. X-r a y Str u ctu r es of
Ru Cl2{dCdC(Z)P h }(d cp m p ) (Z ) H, SiMe3; d cp m p )
C5H3N(CH2P Cy2)2)
Hiroyuki Katayama,* Chikaya Wada, Ken Taniguchi, and Fumiyuki Ozawa*
Department of Applied Chemistry, Graduate School of Engineering, Osaka City University,
Sumiyoshi-ku, Osaka 558-8585, J apan
Received March 28, 2002
Kinetic studies have been carried out for the formation of vinylideneruthenium(II)
complexes RuCl2{dCdC(Z)R}(dcpmp) [Z ) H, R ) p-MeOC6H4 (2a ), p-MeC6H4 (2b), Ph (2c),
p-BrC6H4 (2d ), t-Bu (2e), ferrocenyl (2f); Z ) SiMe3, R ) Ph (5a ), SiMe3 (5b); dcpmp ) 2,6-
bis{(dicyclohexylphosphino)methyl}pyridine] from RuCl2(NCMe)(dcpmp) (1) and alkynes
(RCtCZ). The reactions with terminal alkynes proceed via preliminary dissociation of the
MeCN ligand from 1, giving vinylidene complexes 2a -2f in quantitative yields. More electron-
rich and less sterically demanding alkynes tend to provide higher reaction rates. On the
other hand, the reactions with silylalkynes afford equilibrium mixtures of 1 and â-silylvi-
nylidene complexes 5. The X-ray structures of 2c and 5a are reported.
In tr od u ction
via a 1,2-hydrogen shift (eq 1). A similar tautomeriza-
It has become apparent that ruthenium-catalyzed
organic transformation of alkynes often involves vi-
nylidene intermediates.1 Representative reactions in-
clude homo- and co-dimerization of terminal alkynes,2
cross-coupling reactions of alkynes with alkenes,3 cy-
cloaromatization of conjugated enediynes,4 cyclocarbo-
nylation of diynes,5 and addition of oxygen-nucleophiles
to alkynes.6-8 It has been also documented that vi-
nylidene complexes of the type RuCl2(dCdCHR)L2 (L
tion process has been observed for silylalkynes, which
undergo 1,2-migration of the silyl group to afford
â-silylvinylidene complexes.10,11 Consequently, catalytic
reactions involving vinylidene intermediates must be
significantly affected by kinetic and thermodynamic
features of the interconversion given in eq 1, while the
) PPri , PCy3) serve as good catalyst precursors for ring-
3
opening metathesis polymerization of cycloalkenes and
ring-closing metathesis reactions of R,ω-dienes.9 Vi-
nylidene complexes responsible for these catalyses are
generally afforded by tautomerization of alkyne ligands
(7) (a) Doucet, H.; Derrien, N.; Kabouche, Z.; Bruneau, C.; Dixneuf,
P. H. J . Organomet. Chem. 1997, 551, 151-157. (b) Gemel, C.;
Trimmel, G.; Slugovc, C.; Kremel, S.; Mereiter, K.; Schmid, R.;
Kirchner, K. Organometallics 1996, 15, 3998-4004. (c) Doucet, H.;
Martin-Vaca, B.; Bruneau, C.; Dixneuf, P. H. J . Org. Chem. 1995, 60,
10901-10912. (d) Ho¨fer, J .; Doucet, H.; Bruneau, C.; Dixneuf, P. H.
Tetrahedron Lett. 1991, 32, 7409-7410. (e) Mahe´, R.; Sasaki, Y.;
Bruneau, C.; Dixneuf, P. H. J . Org. Chem. 1989, 54, 1518-1523. (f)
Mahe´, R.; Dixneuf, P. H.; Le´colier, S. Tetrahedron Lett. 1986, 27, 6333-
6336.
(8) (a) Suzuki, T.; Tokunaga, M.; Wakatsuki, Y. Org. Lett. 2001, 3,
735-737. (b) Tokunaga, M.; Wakatsuki, Y. Angew. Chem., Int. Ed.
1998, 37, 2867-286.
(9) (a) Katayama, H.; Urushima, H.; Ozawa, F. J . Organomet. Chem.
2000, 606, 16-25. (b) Katayama, H.; Urushima, H.; Ozawa, F. Chem.
Lett. 1999, 369-370. (c) Katayama, H.; Ozawa, F. Chem. Lett. 1998,
67-68.
(10) For ruthenium, see: (a) Katayama, H.; Ozawa, F. Organome-
tallics 1998, 17, 5190-5196. (b) Huang, D.; Streib, W. E.; Bollinger,
J . C.; Caulton, K. G.; Winter, R. F.; Scheiring, T. J . Am. Chem. Soc.
1999, 121, 8087-8097.
(11) For other transition metals, see: (a) Foerstner, J .; Kakoschke,
A.; Goddard, R.; Rust, J .; Wartchow, R.; Butenscho¨n, H. J . Organomet.
Chem. 2001, 617-618, 412-422. (b) Gauss, C.; Veghini, D.; Berke, H.
Chem. Ber./ Recl. 1997, 130, 183-194. (c) Connelly, N. G.; Geiger, W.
E.; Lagunas, M. C.; Metz, B.; Rieger, A. L.; Rieger, P. H.; Shaw, M. J .
Am. Chem. Soc. 1995, 117, 12202-12208. (d) Naka, A.; Okazaki, S.;
Hayasi, M.; Ishikawa, M. J . Organomet. Chem. 1995, 499, 35-41. (e)
Werner, H.; Baum, M.; Schneider, D.; Windmu¨ller, B. Organometallics
1994, 13, 1089-1097. (f) Sakurai, H.; Fujii, T.; Sakamoto, K. Chem.
Lett. 1992, 339-342.
* To whom correspondence should be addressed. Fax: +81
666052978. E-mail: katayama@a-chem.eng.osaka-cu.ac.jp; ozawa@
a-chem.eng.osaka-cu.ac.jp.
(1) For a review, see: Bruneau, C.; Dixneuf, P. H. Acc. Chem. Res.
1999, 32, 311-323.
(2) (a) Baratta, W.; Del Zotto, A.; Herdtweck, E.; Vuano, S.; Rigo,
P. J . Organomet. Chem. 2001, 617-618, 511-519. (b) Tenorio, M. A.
J .; Tenorio, M. J .; Puerta, M. C.; Valerga, P. Organometallics 2000,
19, 1333-1342. (c) Bassetti, M.; Marini, S.; Tortorella, F.; Cadierno,
V.; D´ıez, J .; Gamasa, M. P.; Gimeno, J . J . Organomet. Chem. 2000,
593-594, 292-298. (d) Baratta, W.; Herrmann, W. A.; Rigo, P.;
Schwarz, J . J . Organomet. Chem. 2000, 593-594, 489-493. (e)
Nishibayashi, Y.; Yamanashi, M.; Wakiji, I.; Hidai, M. Angew. Chem.,
Int. Ed. 2000, 39, 2909-2911. (f) Yi, C. S.; Liu, N. Organometallics
1998, 17, 3158-3160. (g) Qu¨, J .-P.; Masui, D.; Ishii, Y.; Hidai, M. Chem.
Lett. 1998, 1003-1004. (h) Yi, C. S.; Liu, N.; Rheingold, A. L.; Liable-
Sands, L. M. Organometallics 1997, 16, 3910-3913, and references
therein.
(3) Murakami, M.; Ubukata, M.; Ito, Y. Tetrahedron Lett. 1998, 39,
7361-7364.
(4) Wang, Y.; Finn, M. G. J . Am. Chem. Soc. 1995, 117, 8045-8046.
(5) Onitsuka, K.; Katayama, H.; Sonogashira, K.; Ozawa, F. J .
Chem. Soc., Chem. Commun. 1995, 2267-2268.
(6) (a) Trost, B. M.; Vidal, B.; Thommen, M. Chem. Eur. J . 1999, 5,
1055-1069. (b) Trost, B. M.; Kulawiec, R. J . J . Am. Chem. Soc. 1992,
114, 5579-5584. (c) Trost, B. M.; Dyker, G.; Kulawiec, R. J . Am. Chem.
Soc. 1990, 112, 7809-7811.
10.1021/om020238r CCC: $22.00 © 2002 American Chemical Society
Publication on Web 06/25/2002

3286 Organometallics, Vol. 21, No. 15, 2002
Katayama et al.
Ta ble 1. P seu d o-F ir st-Or d er Ra te Con sta n ts for
th e Rea ction of 1 w ith P h CtCH in ClCH2CH2Cl a t
50 °Ca
detailed information on this process, particularly on the
effects of substituent R, has so far been extremely
limited.12
run
[PhCtCH] (mM)
[MeCN] (mM)b
104kobsd (s-1
)
Previously, we examined interconversion between
silylalkyne and â-silylvinylidene complexes of rhodium
by kinetic experiments. This study revealed that ther-
modynamic stability of vinylidene complexes increases
as the R substituent becomes more electron-donating.13
The present paper reports a related study on ruthenium
complexes. Using 2,6-bis{(dicyclohexylphosphino)methyl}-
pyridine (dcpmp) as a supporting ligand, we could
observe kinetic and thermodynamic data for alkyne-
vinylidene interconversion on ruthenium.
1
2
3
4
5
160
210
300
320
380
150
74
74
74
74
74
0
2.67(3)
3.5(1)
4.75(4)
5.04(5)
5.67(6)
9.6(3)
6
7
8
9
10
11
12c
150
150
150
150
19
40
60
79
127
40
8.86(9)
4.71(6)
3.8(1)
2.74(9)
1.78(4)
2.79(4)
150
150 (PhCtCD)
Resu lts
a
b
Initial concentration: [1]0 ) 15 mM. The concentration of
free MeCN added to the system. c The reaction was performed with
PhCtCD instead of PhCtCH.
Rea ction s of Ru Cl2(NCMe)(d cp m p ) (1) w ith Ter -
m in a l Alk yn es. A simple and clean reaction system is
needed to perform kinetic investigations. After several
attempts, we found RuCl2(NCMe)(dcpmp) (1) as the
starting material of choice in this respect. This complex
cleanly reacts with a variety of terminal alkynes at
convenient reaction temperatures for kinetic experi-
ments, giving the corresponding vinylidene complexes
(2a -2f) in quantitative yields (eq 2).
F igu r e 1. Effect of PhCtCH concentration on the reaction
rate of 1 with PhCtCH in ClCH2CH2Cl at 50 °C in the
presence of added MeCN. Initial concentration: [1]0 ) 15
mM, [MeCN]0 ) 74 mM.
formation of vinylidene complex 2c obeyed good pseudo-
first-order kinetics over 85% conversion of 1. Table 1
lists the rate constants measured at various reaction
conditions. No ruthenium species other than 1 and 2c
were detected in all kinetic runs.
The reaction rate increased with increasing concen-
tration of PhCtCH (runs 1-5). A good linear correlation
(r ) 1.000) was observed between 1/kobsd and 1/[PhCt
CH] values (Figure 1). On the other hand, the reaction
was effectively retarded by addition of free MeCN to the
system (runs 6-11); the 1/kobsd values were linearly
correlated with the concentration of added MeCN
(Figure 2, r ) 0.998). Furthermore, a moderate kinetic
isotope effect (kH/kD ) 1.69(5)) was noted in the reaction
with deuterated phenylacetylene (run 12).
These kinetic observations clearly suggest the mech-
anism depicted in Scheme 1. The coordinatively satu-
rated complex 1 undergoes reversible dissociation of the
MeCN ligand. The five-coordinate intermediate 3 thus
generated subsequently reacts with PhCtCH to give the
vinylidene complex 2c, very probably via a phenylacety-
lene-coordinated intermediate 4c. Steady-state approxi-
mation for the concentration of 3 leads to the kinetic
expressions given in eqs 3 and 4, in which the rate
constants k1 and k-1 correspond to the forward and
Complex 1 was prepared in 65% isolated yield by
treating [RuCl2(p-cymene)]2 with dcpmp (1 equiv/Ru) in
toluene in the presence of excess MeCN (10 equiv/Ru)
at 80 °C for 22 h and identified by NMR spectroscopy
and elemental analysis. The 31P{1H} NMR spectrum
exhibited a sharp singlet at δ 44.6. The 1H NMR
spectrum was consistent with a C2v symmetrical struc-
ture involving meridional coordination of the PNP
ligand. Thus the PCH2 protons were observed as a
virtual triplet at δ 3.72 (J app ) 4.2 Hz), showing a trans
arrangement of the two phosphorus atoms. The signals
arising from the pyridine ring appeared at δ 7.23 and
7.04 in an apparent AX2 pattern (3J HH ) 7.5 Hz). The
presence of the MeCN ligand was clearly indicated by
the occurrence of a methyl proton signal at δ 2.35 in
1
the H NMR spectrum and of a ν(CtN) absorption at
2265 cm-1 in the IR spectrum.
The reaction of 1 with PhCtCH (>10 equiv) in ClCH2-
CH2Cl was followed by 31P{1H} NMR spectroscopy. The
(12) (a) Ajioka, Y.; Matsushima, Y.; Onitsuka, K.; Yamazaki, H.;
Takahashi, S. J . Organomet. Chem. 2001, 617-618, 601-615. (b) de
los R´ıos, I.; Tenorio, M. J .; Puerta, M. C.; Valerga, P. J . Am. Chem.
Soc. 1997, 119, 6529-6538.
(13) Katayama, H.; Onitsuka, K.; Ozawa, F. Organometallics 1996,
15, 4642-4645.

Vinylideneruthenium(II) Complexes
Organometallics, Vol. 21, No. 15, 2002 3287
Ta ble 2. P seu d o-F ir st-Or d er Ra te Con sta n ts for
th e Rea ction s of 1 w ith Va r iou s Ter m in a l Alk yn esa
run
alkyne
product
104kobsd (s-1
)
1
2
3
4
5
6
7
p-MeOC6H4CtCH
p-MeC6H4CtCH
PhCtCH
p-BrC6H4CtCH
p-MeO2CC6H4CtCH
t-BuCtCH
2a
2b
2c
2d
6.06(8)
4.14(3)
4.71(6)
2.89(4)
very slow
3.10(4)
7.4(2)
2e
2f
FcCtCH
a
All reactions were run in ClCH2CH2Cl at 50 °C. Initial
concentration: [1]0 ) 15 mM, [alkyne]0 ) 150 mM, [MeCN]0 ) 40
mM.
F igu r e 2. Effect of added MeCN on the reaction rate of 1
with PhCtCH in ClCH2CH2Cl at 50 °C. Initial concentra-
tion: [1]0 ) 15 mM, [PhCtCH]0 ) 150 mM.
Sch em e 1
F igu r e 3. Time course of the reaction of 1 with Me3SiCt
CSiMe3 in ClCH2CH2Cl at 50 °C. Initial concentration: [1]0
) 15 mM, [Me3SiCtCSiMe3]0 ) 0.15 M.
to the higher reaction rate (runs 1-5). tert-Butylacety-
lene is moderately reactive probably due to its bulkiness
(run 6), while ferrocenylacetylene (FcCtCH) exhibits
the highest reactivity (run 7).
Rea ction s of Ru Cl2(NCMe)(d cp m p ) (1) w ith Si-
lyla lk yn es. Unlike the reactions of terminal alkynes,
the reactions of 1 with silylalkynes afforded equilibrium
mixtures of 1 and â-silylvinylidene complexes (eq 5).
Figure 3 shows the time course of the reaction of 1 with
backward reactions between 1 and 3, respectively, and
k2 to the overall process from 3 to 2c.
d[1] d[2c]
-
)
) kobsd[1] )
k1k2[PhCtCH]
k-1[MeCN] + k2[PhCtCH]
dt
dt
[1] (3)
k-1[MeCN]
1
kobsd
1
k1
)
+
(4)
k1k2[PhCtCH]
On the basis of the slope and intercept of the plot in
Figure 1, the values of k1 and k-1/k2 are estimated as
3.0 × 10-3 s-1 and 22, respectively, which are in good
agreement with the values derived from the plot in
Figure 2 (k1 ) 2.9 × 10-3 s-1, k-1/k2 ) 18). The k1 value
corresponds to ∆Gq ) 22.7 kcal mol-1. On the other
323
hand, the k-1/k2 ratio indicates that the re-coordination
of MeCN to 3 to give 1 is easier by 1.9 kcal mol-1 than
the conversion of 3 into 2c. These kinetic features, in
conjunction with the observation of a clear deuterium
kinetic isotope effect, clearly suggest a significant
contribution of the rate of phenylacetylene-phenylvi-
nylidene tautomerization toward the kobsd value, even
though the dissociation of MeCN from 1 constitutes the
slowest step in the overall process.
Table 2 compares the reactivity of seven kinds of
terminal alkynes under the same reaction conditions.
There is a tendency that the more electron-donating
substituent at the para position of phenylacetylene leads
Me3SiCtCSiMe3 in ClCH2CH2Cl at 50 °C. The conver-
sion of 1 into 5b obeyed pseudo-first-order kinetics (kobsd
) 0.24 × 10-4 sec-1) over 10 h to reach the equilibrium
with K(5b/1) ) [5b][MeCN]/[1][Me3SiCtCSiMe3] ) 11.3
× 10-3 (∆G323 ) 2.9 kcal mol-1). Almost the same
equilibrium constant (12 × 10-3) was observed for the
reverse reaction system starting from 5b and MeCN (1
equiv). A similar set of experiments was carried out for
the interconversion between 1 and 5a , and the following
equilibrium constant was obtained: K(5a /1) ) [5a ]-
[MeCN]/[1][PhCtCSiMe3] ) 3.9 × 10-3 (∆G323 ) 3.5

3288 Organometallics, Vol. 21, No. 15, 2002
Katayama et al.
Ta ble 3. Ch a r a cter istic NMR Da ta for 2a -2f, 5a ,
a n d 5ba
1H NMR
Hâ
13C{1H} NMRb
complex
CR
Câ
31P{1H} NMR
2a
2b
2c
2d
2e
2f
5.08 (s)
5.06 (s)
5.09 (s)
4.98 (s)
3.69 (s)
4.72 (s)
363.6 (t, 12) 112.1 (s)
363.3 (t, 11) 112.3 (s)
362.0 (t, 11) 112.5 (s)
361.0 (t, 12) 111.3 (s)
361.8 (t, 12) 118.2 (s)
360.3 (t, 11) 107.7 (s)
340.8 (t, 12) 110.3 (s)
46.7 (s)
46.4 (s)
46.1 (s)
45.7 (s)
43.6 (s)
48.5 (s)
44.0 (s)
40.9 (s)
5a
5b
c
c
a
In CDCl3 at 20 °C. Chemical shifts are reported in δ (ppm).
Numbers in parentheses are J PC values in Hz. c 13C{1H} NMR
b
2
analysis was not feasible due to low solubility of the complex.
Ta ble 4. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) a n d Dih ed r a l An gles betw een Lea st-Squ a r es
P la n es (d eg) for 2c a n d 5a
F igu r e 4. Molecular structure of RuCl2{dCdC(H)Ph}-
(dcpmp) (2c). Thermal ellipsoids are drawn at the 50%
probability level. Solvent molecule is omitted for clarity.
2c
5a
Ru-C(1)
Ru-Cl(1)
Ru-Cl(2)
Ru-N
Ru-P(1)
Ru-P(2)
C(1)-C(2)
1.816(6)
2.427(1)
2.418(1)
2.218(4)
2.375(2)
2.355(2)
1.310(8)
1.845(4)
2.4152(9)
2.4023(9)
2.200(3)
2.3595(9)
2.3635(9)
1.301(5)
Ru-C(1)-C(2)
Cl(1)-Ru-Cl(2)
P(1)-Ru-P(2)
N-Ru-C(1)
172.3(5)
173.22(5)
160.28(5)
176.5(2)
177.2(3)
167.22(3)
162.10(3)
179.4(1)
(Ru, Cl(1), Cl(2), C(1))
vs
63.48(3)
4.99(9)
(C(1), C(2), C(3))
kcal mol-1). Thus the slightly higher stability of 5b than
5a was suggested.
The reaction of 1 was tested also with FcCtCSiMe3,
p-MeOC6H4CtCSiMe3, and p-MeO2CC6H4CtCSiMe3.
While the formation of the vinylidene complex was noted
for all silylalkynes by NMR spectroscopy, partial desi-
lylation giving nonsilylated vinylidene complexes si-
multaneously took place,10a and no reproducible data
were therefore obtained.
The â-silylvinylidene complex 5a was found to be
much less stable than 2c derived from phenylacetylene
as a terminal alkyne. Thus the treatment of 5a with
phenylacetylene in ClCH2CH2Cl at 50 °C resulted in
quantitative formation of 2c, while the reverse reaction
of 2c with PhCtCSiMe3 did not take place.
F igu r e 5. Molecular structure of RuCl2{dCdC(SiMe3)-
Ph}(dcpmp) (5a ). Thermal ellipsoids are drawn at the 50%
probability level.
ligand (2J PC ) 11 or 12 Hz), whereas the â-carbon was
a singlet. Complexes 2a -2f exhibited a singlet signal
at δ 5.09-3.69 assignable to the vinylidene proton.
Although 13C{1H} NMR analysis of 5b was not feasible
owing to its low solubility, the presence of the vinylidene
ligand was clearly indicated by the appearance of strong
νCdC absorptions at 1605 and 1560 cm-1 in the IR
spectrum.
Complexes 2c and 5a were further examined by
single-crystal X-ray diffraction analysis. Selected struc-
tural parameters are listed in Table 4. ORTEP diagrams
are given in Figures 4 and 5. Both complexes adopt a
distorted octahedral configuration with meridional co-
ordination of the dcpmp ligand. The two chloro ligands
are oriented in mutually trans positions, while the
vinylidene ligand is situated trans to the pyridyl group
of dcpmp.
Id en tifica tion of Vin ylid en e Com p lexes. We have
described the formation of 2a -2f, 5a , and 5b from 1.
These complexes could be synthesized more conve-
niently starting from [RuCl2(p-cymene)]2 (eq 6). Reac-
tions of the p-cymene complex with dcpmp and alkynes
in toluene proceeded at 80 °C to afford the vinylidene
complexes in 94-40% isolated yields.
The Ru-C(1) distances of 2c (1.816(6) Å) and 5a
(1.845(4) Å) are in a typical range of six-coordinate
vinylideneruthenium(II) complexes,14 but significantly
longer than that of five-coordinate complexes having a
square pyramidal structure with the vinylidene ligand
Table 3 lists the selected NMR data. The 13C{1H}
NMR spectra exhibited characteristic signals of R- and
â-vinylidene carbons at δ 363.6-340.8 and 118.2-107.7,
respectively. The R-carbon was observed as a triplet due
to coupling with the two phosphorus nuclei of the dcpmp
(14) (a) Bruce, M. I. Chem. Rev. 1991, 91, 197-257. (b) Bruce, M.
I.; Swincer, A. G. Adv. Organomet. Chem. 1983, 22, 59-128.

Vinylideneruthenium(II) Complexes
Organometallics, Vol. 21, No. 15, 2002 3289
ular sieves (MS4A), which were activated by heating at ca.
300 °C under vacuum overnight prior to use. CDCl3 was
purified by passage through an alumina column, degassed by
freeze-pump-thaw cycles, and stored over activated MS4A
in the dark. Liquid alkynes were degassed by freeze-pump-
thaw cycles prior to use. [RuCl2(p-cymene)]2,17 p-MeOC6H4Ct
CH,18 p-BrC6H4CtCH,19 and FcCtCH20 were synthesized
according to the literatures. All other chemicals were obtained
from commercial suppliers and used without further purifica-
tion.
at the apical position: RuBr2(dCdCHPh)(PPh3)2 (1.768-
(17) Å),15 RuCl2(dCdCHPh)(PPri3)2 (1.750(4) Å),10a RuCl2-
(dCdCHPh)(PCy3)2 (1.761(2) Å),10a and RuCl2{dCd
C(SePri)Ph}(PPh3)2 (1.769(5) Å).16 On the other hand,
the C(1)-C(2) bond of the vinylidene ligand in 2c (1.310-
(8) Å) and 5a (1.301(5) Å) is apparently shorter than
that of the five-coordinate complexes (1.33-1.36 Å).
Thus the coordination of the pyridine donor in 2c and
5a elongates the Ru-C(1) bond to reduce the π-back-
donation from ruthenium to the vinylidene ligand,
leading to the shorter C(1)-C(2) bond than that in the
five-coordinate analogues.
Syn th esis of 2,6-Bis{(d icycloh exylp h osp h in o)m eth yl}-
p yr id in e (d cp m p ). To a solution of dicyclohexylphosphine
(2.65 g, 13.4 mmol) in THF (25 mL) was added dropwise a
solution of n-butyllithium in hexane (1.6 M, 8.5 mL, 14 mmol)
at -78 °C. The mixture was stirred at room temperature for
1 h to give a pale yellow solution of lithium dicyclohexylphos-
phide. This solution was added dropwise through a cannula
to a solution of 2,6-bis(chloromethyl)pyridine (1.18 g, 6.70
mmol) in THF (20 mL) at 0 °C. The resulting orange solution
was stirred at room temperature for 18 h. Methanol (6 mL)
was slowly added, and then the mixture was concentrated by
pumping to dryness. The yellowish white solid thus obtained
was extracted with CH2Cl2 (5 mL × 2), and the extract was
filtered through a short column of alumina. The combined
filtrate was evaporated by pumping. The residue was washed
with methanol (15 mL × 3) and dried under vacuum to give a
Discu ssion
We could measure the rates of formation of vinylidene
complexes 2 from 1 and terminal alkynes (Table 2).
While the reactivity is affected by both the electronic
and steric nature of the R groups, the kinetic data
observed for five kinds of phenylacetylene derivatives
(p-YC6H4CtCH) reveal that the more electron-donating
substituent Y tends to give the higher reaction rate
(runs 1-5). As described in Scheme 1 using pheny-
lacetylene as a substrate, vinylidene complexes 2 are
formed by the sequence of three elementary processes
(i.e., dissociation of MeCN, coordination of alkyne, and
tautomerization of alkyne ligand into vinylidene ligand).
Of these elementary processes, the dissociation of MeCN
is independent of alkynes, whereas the rates of the other
processes must be dependent on the nature of the
alkynes. Since the formation of alkyne complexes 4 is
easier for more electron-deficient alkynes in a general
sense, we may consider that the variation in the reaction
rates of five phenylacetylene derivatives is mainly due
to the rate difference in the final elementary process
leading to the tautomerization of alkyne ligand into
vinylidene ligand. This consideration is also supported
by the kinetic findings for the reaction of phenylacety-
lene (k-1/k2 ) 20(2), kH/kD ) 1.69(5)). Therefore, we may
conclude that, at least for the phenylacetylene deriva-
tives, the alkyne-vinylidene tautomerization is facili-
tated by increasing electron-donating ability of the R
groups.
1
white solid of dcpmp (1.76 g, 53%). Mp: 59-60 °C. H NMR
(CDCl3): δ 7.42 (t, J ) 7.5 Hz, 1H, H4 of pyridine ring), 7.08
2
(d, J ) 7.5 Hz, 2H, H3,5 of pyridine ring), 2.95 (d, J PH ) 2.1
Hz, 4H, PCH2), 1.90-1.56, 1.39-1.05 (each m, 44H, Cy). 13C-
2
{1H} NMR (CDCl3): δ 159.9 (d, J PC ) 10 Hz, C2,6 of pyridine
3
ring), 135.9 (s, C4 of pyridine ring), 120.2 (d, J PC ) 9 Hz, C3,5
1
1
of pyridine ring), 33.4 (d, J PC ) 14 Hz, PCH2), 31.9 (d, J PC
)
21 Hz, C1 of Cy), 29.8 (d, J PC ) 14 Hz, C2,6 of Cy), 29.0 (d,
3J PC ) 9 Hz, C3,5 of Cy), 26.4 (s, C4 of Cy). 31P{1H} NMR
(CDCl3): δ 3.8 (s). Anal. Calcd for C31H51NP2: C, 74.51; H,
10.29; N, 2.80. Found: C, 74.31; H, 10.24; N, 3.04.
2
Syn th esis of Aceton itr ile Com p lex 1. To a suspension
of [RuCl2(p-cymene)]2 (370 mg, 0.604 mmol) in toluene (20 mL)
were added dcpmp (605 mg, 1.21 mmol) and acetonitrile (0.64
mL, 12 mmol) at room temperature. The mixture was stirred
at 80 °C for 22 h and then cooled to room temperature. The
orange microcrystalline solid of 1 thus precipitated was
collected by filtration through a filter-paper-tipped cannula,
washed with pentane (5 mL × 3), and dried under vacuum
(0.557 g, 65%). Mp: 280-283 °C (dec). 1H NMR (CDCl3): δ
7.23 (t, J ) 7.5 Hz, H4 of pyridine ring), 7.04 (d, J ) 7.5 Hz,
H3,5 of pyridine ring), 3.72 (virtual triplet, J app ) 4.2 Hz, 4H,
PCH2), 2.60-2.51, 2.00-1.66, 1.38-1.22 (each m, 44H, Cy),
2.35 (s, 3H, MeCN). 13C{1H} NMR (CDCl3): δ 166.2 (virtual
triplet, J app ) 5 Hz, C2,6 of pyridine ring), 134.1 (s, C4 of
pyridine ring), 125.7 (s, RuNCMe), 119.3 (virtual triplet, J app
) 5 Hz, C3,5 of pyridine ring), 37.8 (virtual triplet, J app ) 9
Hz, PCH2), 34.8 (virtual triplet, J app ) 9 Hz, C1 of Cy), 29.3,
Exp er im en ta l Section
Gen er a l P r oced u r e a n d Ma ter ia ls. All manipulations
were performed under a nitrogen atmosphere using conven-
tional Schlenk techniques. Nitrogen gas was purified by
passing through a column of P2O5 (Merck, SICAPENT). NMR
spectra were recorded on a Varian Mercury 300 (1H NMR,
300.11 MHz; 13C NMR, 75.46 MHz; 31P NMR, 121.49 MHz)
spectrometer. Chemical shifts are reported in δ (ppm), refer-
enced to the 1H (of residual protons) and 13C signals of
deuterated solvents or to the 31P signal of external 85% H3-
PO4. The symbol J app stands for the apparent coupling constant
for a virtually coupled signal. IR spectra were recorded on a
J ASCO FT/IR-410 instrument. Mass spectra were measured
with a Shimadzu QP-5000 GC-mass spectrometer (EI, 70 eV).
CH2Cl2, ClCH2CH2Cl, and MeCN were dried over CaH2.
Methanol was dried with Mg(OMe)2. THF and toluene were
dried over sodium benzophenone ketyl. These solvents were
distilled under a nitrogen atmosphere and stored over molec-
28.8 (each s, C3,5 of Cy), 27.6, 27.2 (each virtual triplet, J app
)
6 Hz, C2,6 of Cy), 26.1 (s, C4 of Cy), 4.7 (s, RuNCMe). 31P{1H}
NMR (CDCl3): δ 44.6 (s). IR (KBr): 2265 cm-1. Anal. Calcd
for C33H54Cl2N2P2Ru: C, 55.61; H, 7.64; N, 3.93. Found: C,
55.40; H, 7.70; N, 4.07.
Rea ction of 1 w ith Alk yn es. A typical procedure (entry 1
in Table 1) is as follows. A 5 mm NMR sample tube equipped
with a rubber septum cap was charged with 1 (7.6 mg, 11
µmol), and the system was replaced with nitrogen gas. 1,2-
Dichloroethane (0.7 mL) was added by syringe, and the
(17) Bennett, M. A.; Smith, A. K. J . Chem. Soc., Dalton Trans. 1974,
233-241.
(18) Takahashi, S.; Kuroyama, Y.; Sonogashira, K.; Hagihara, N.
Synthesis 1980, 627-630.
(15) Wakatsuki, Y.; Koga, N.; Yamazaki, H.; Morokuma, K. J . Am.
Chem. Soc. 1994, 116, 8105-8111.
(16) Hill, A. F.; Hulkes, A. G.; White, A. J . P.; Williams, D. J .
Organometallics 2000, 19, 371-373.
(19) J acobs, T. L. Org. React. 1949, 5, 50-51.
(20) Doisneau, G.; Balavoine, G.; Fillebeen-Khan, T. J . Organomet.
Chem. 1992, 425, 113-117.

3290 Organometallics, Vol. 21, No. 15, 2002
Katayama et al.
mixture was gently shaken until all the complex dissolved. To
the resulting yellow solution were succesively added MeCN
(1.1 mg, 27 µmol) and PhCtCH (10.7 mg, 0.105 mmol) at room
temperature. The sample was immediately inserted into an
NMR probe preheated at 50 ( 0.1 °C and kept at this
temperature throughout the experiment. The time course of
the reaction was followed by measuring relative peak integra-
tion of 1 (δ 44.5) and 2c (δ 46.0) in the 31P{1H} NMR spectra.
Syn th esis of Vin ylid en e Com p lexes 2a -2f, 5a , a n d 5b.
A typical procedure is as follows. A mixture of [RuCl2(p-
cymene)]2 (204 mg, 0.333 mmol), dcpmp (334 mg, 0.668 mmol),
and PhCtCH (68 mg, 0.67 mmol) in toluene (11 mL) was
heated at 80 °C for 32 h with vigorous stirring. An initially
red suspension was gradually changed into a dark red solution,
which was allowed to stand at room temperature and then at
-20 °C overnight to yield a reddish brown precipitate of 2c,
which was collected by filtration, washed with toluene (2 mL),
and dried under vacuum (483 mg, 94%). This product was
spectroscopucally pure. An analytically pure crystalline com-
pound was obtained by slow diffusion of a CH2Cl2 solution into
hexane. The other vinylidene complexes were similarly pre-
pared. For 2e an excess amount (10 equiv/Ru) of tert-buty-
lacetylene was nescessary.
C4 of Cy); 31P{1H} NMR (CDCl3) δ 46.1 (s); IR (KBr) 1617, 1591
cm-1. Anal. Calcd for C39H57Cl2NP2Ru: C, 60.54; H, 7.42; N,
1.81. Found: C, 60.80; H, 7.50; N, 1.79.
Ru Cl2{dCdC(H)C6H4Br -p}(d cp m p ) (2d ): brown solid
1
(95%); mp 125-128 °C (dec); H NMR (CDCl3) δ 7.65 (t, J )
7.5 Hz, 1H, H4 of pyridine ring), 7.31 (d, J ) 7.5 Hz, 2H, H3,5
of pyridine ring), 7.26, 7.06 (each d, J ) 8.4 Hz, 4H, C6H4),
4.98 (s, 1H, dCdCH), 3.91 (virtual triplet, J app ) 4.2 Hz, 4H,
PCH2), 2.59-2.44, 2.16-1.42, 1.33-1.12 (each m, 44H, Cy);
2
13C{1H} NMR (CDCl3) δ 361.0 (t, J PC ) 12 Hz, RudCdC),
161.3 (virtual triplet, J app ) 4 Hz, C2,6 of pyridine ring), 138.6
(s, C4 of pyridine ring), 131.9, 130.9, 127.3 (each s, C2-6 of C6H4-
Br), 121.0 (virtual triplet, J app ) 4 Hz, C3,5 of pyridine ring),
116.4 (s, C1 of C6H4Br), 111.3 (s, RudCdC), 38.1 (virtual
triplet, J app ) 11 Hz, C1 of Cy), 34.5 (virtual triplet, J app ) 10
Hz, PCH2), 29.5, 28.9 (each s, C3,5 of Cy), 27.5, 27.2 (each
virtual triplet, J app ) 6 Hz, C2,6 of Cy), 26.0 (s, C4 of Cy); 31P-
{1H} NMR (CDCl3) δ 45.7 (s); IR (KBr) 1625, 1600 cm-1. Anal.
Calcd for C39H56BrCl2NP2Ru: C, 54.93; H, 6.62; N, 1.64.
Found: C, 55.66; H, 6.05; N, 1.59.
Ru Cl2{dCdC(H)Bu t}(d cp m p ) (2e): reddish brown solid
1
(76%); mp 95-97 °C; H NMR (CDCl3) δ 7.58 (t, J ) 7.7 Hz,
1H, H4 of pyridine ring), 7.27 (d, J ) 7.7 Hz, 2H, H3,5 of
pyridine ring), 5.30 (s, 2H, CH2Cl2), 3.90 (virtual triplet, J app
) 4.2 Hz, 4H, PCH2), 3.69 (s, 1H, RudCdCH), 2.60-2.48,
2.31-2.20, 2.06-1.95, 1.90-1.46, 1.36-1.13 (each m, 44H, Cy),
Ru Cl2{dCdC(H)C6H4OMe-p}(d cp m p ) (2a ): gray solid
1
(40%); mp 230-232 °C (dec); H NMR (CDCl3) δ 7.63 (t, J )
7.7 Hz, 1H, H4 of pyridine ring), 7.30 (d, J ) 7.7 Hz, 2H, H3,5
of pyridine ring), 7.13, 6.77 (each d, J ) 8.2 Hz, 4H, C6H4),
5.08 (s, 1H, dCdCH), 3.91 (virtual triplet, J app ) 4.1 Hz, 4H,
PCH2), 3.77 (s, 3H, OMe), 2.61-2.42, 2.14-1.42, 1.32-1.13
(each m, 44H, Cy); 13C{1H} NMR (CDCl3) δ 363.6 (t, 2J PC ) 12
Hz, RudCdC), 161.3 (virtual triplet, J app ) 4 Hz, C2,6 of
pyridine ring), 156.6 (s, C4 of C6H4OMe), 138.4 (s, C4 of pyridine
ring), 127.3, 113.7 (each s, C2,3,5,6 of C6H4OMe), 124.0 (s, C1 of
C6H4OMe), 120.9 (virtual triplet, J app ) 4 Hz, C3,5 of pyridine
ring), 112.1 (s, RudCdC), 55.3 (s, OMe), 38.2 (virtual triplet,
J app ) 11 Hz, C1 of Cy), 34.5 (virtual triplet, J app ) 10 Hz,
PCH2), 29.4, 28.8 (each s, C3,5 of Cy), 27.5, 27.2 (each virtual
triplet, J app ) 6 Hz, C2,6 of Cy), 26.0 (s, C4 of Cy); 31P{1H} NMR
(CDCl3) δ 46.7 (s); IR (KBr) 1623, 1599 cm-1. Anal. Calcd for
2
1.20 (s, t-Bu); 13C{1H} NMR (CDCl3) δ 361.8 (t, J PC ) 12 Hz,
RudCdC), 161.9 (virtual triplet, J app ) 4 Hz, C2,6 of pyridine
ring), 138.2 (s, C4 of pyridine ring), 120.6 (virtual triplet, J app
3
) 4 Hz, C3,5 of pyridine ring), 118.2 (t, J PC ) 2 Hz, RudCd
C), 54.2 (s, CH2Cl2), 38.6 (virtual triplet, J app ) 10 Hz, C1 of
Cy), 34.8 (virtual triplet, J app ) 10 Hz, PCH2), 32.6 (s, C(CH3)3),
31.2 (s, C(CH3)3), 29.7, 29.0 (each s, C3,5 of Cy), 27.5, 27.2 (each
virtual triplet, J app ) 6 Hz, C2,6 of Cy), 26.1 (s, C4 of Cy); 31P-
{1H} NMR (CDCl3) δ 43.6 (s); IR (KBr) 1602, 1571 cm-1. Anal.
Calcd for C37H61Cl2NP2Ru‚CH2Cl2: C, 54.42; H, 7.57; N, 1.67.
Found: C, 54.21; H, 6.98; N, 1.21.
Ru Cl2{dCdC(H)F c}(d cp m p ) (2f): dark brown solid (58%);
1
mp 263-265 °C (dec); H NMR (CDCl3) δ 7.60 (t, J ) 7.5 Hz,
1H, H4 of pyridine ring), 7.28 (d, J ) 7.5 Hz, 2H, H3,5 of
pyridine ring), 4.72 (s, 1H, RudCdCH), 4.16, 4.03 (each s, 4H,
C5H4Fe), 4.12 (s, 5H, C5H5Fe), 3.88 (virtual triplet, J app ) 4.2
Hz, 4H, PCH2), 3.69 (s, 1H, RudCdCH), 2.60-2.42, 2.20-2.08,
1.98-1.40, 1.36-1.13 (each m, 44H, Cy); 13C{1H} NMR (CDCl3)
δ 360.3 (t, 2J PC ) 11 Hz, RudCdC), 161.3 (virtual triplet, J app
) 4 Hz, C2,6 of pyridine ring), 138.2 (s, C4 of pyridine ring),
C
40H59Cl2NOP2Ru: C, 59.77; H, 7.40; N, 1.74. Found: C, 60.52;
H, 7.88; N, 1.71.
R u Cl2{dCdC(H)C6H4Me-p}(d cp m p ) (2b ): dark green
solid (90%); mp 245-250 °C (dec); 1H NMR (CDCl3) δ 7.63 (t,
J ) 7.7 Hz, 1H, H4 of pyridine ring), 7.30 (d, J ) 7.7 Hz, 2H,
H3,5 of pyridine ring), 7.09, 6.99 (each d, J ) 8.1 Hz, 4H, C6H4),
5.06 (s, 1H, dCdCH), 3.90 (virtual triplet, J app ) 4.2 Hz, 4H,
PCH2), 2.32 (s, 3H, Me), 2.55-2.47, 2.17-1.44, 1.30-1.14 (each
3
120.8 (t, J PC ) 4 Hz, C3,5 of pyridine ring), 107.7 (s, RudCd
2
m, 44H, Cy); 13C{1H} NMR (CDCl3) δ 363.3 (t, J PC ) 11 Hz,
C), 78.7 (s, C1 of C5H4Fe), 69.0 (s, C5H5Fe), 66.9, 66.5 (each s,
C2,3,4,5 of C5H4Fe), 38.3 (virtual triplet, J app ) 10 Hz, C1 of Cy),
34.5 (virtual triplet, J app ) 10 Hz, PCH2), 29.4, 28.9 (each s,
C3,5 of Cy), 27.5, 27.1 (each virtual triplet, J app ) 6 Hz, C2,6 of
Cy), 26.0 (s, C4 of Cy); 31P{1H} NMR (CDCl3) δ 48.5 (s); IR
(KBr) 1630, 1599 cm-1. Anal. Calcd for C43H61Cl2NP2FeRu: C,
58.57; H, 6.97; N, 1.59. Found: C, 57.99; H, 6.82; N, 1.58.
Ru Cl2{dCdC(SiMe3)P h }(d cp m p ) (5a ): reddish brown
solid (59%); mp 184-189 °C (dec); 1H NMR (CDCl3) δ 7.57 (t,
J ) 7.5 Hz, 1H, H4 of pyridine ring), 7.32-7.18 (m, 6H, H3,5 of
pyridine ring and H2,3,5,6 of Ph), 7.00 (t, J ) 7.2 Hz, H4 of Ph),
3.89 (virtual triplet, J app ) 4.0 Hz, 4H, PCH2), 2.56-2.48,
2.26-2.08, 2.04-1.11 (each m, 44H, Cy), 0.27 (s, 9H, SiMe3);
RudCdC), 161.3 (virtual triplet, J app ) 4 Hz, C2,6 of pyridine
ring), 138.4 (s, C4 of pyridine ring), 133.2 (s, C1 of C6H4), 129.0,
128.7, 126.1 (each s, C2-6 of C6H4), 120.9 (virtual triplet, J app
) 4 Hz, C3,5 of pyridine ring), 112.3 (s, RudCdC), 38.2 (virtual
triplet, J app ) 11 Hz, C1 of Cy), 34.5 (virtual triplet, J app ) 10
Hz, PCH2), 29.4, 28.8 (each s, C3,5 of Cy), 27.5, 27.2 (each
virtual triplet, J app ) 6 Hz, C2,6 of Cy), 26.0 (s, C4 of Cy), 21.1
(s, Me); 31P{1H} NMR (CDCl3) δ 46.4 (s); IR (KBr) 1623, 1603
cm-1. Anal. Calcd for C40H59Cl2NP2Ru: C, 60.98; H, 7.55; N,
1.78. Found: C, 61.18; H, 7.78; N, 1.75.
Ru Cl2{dCdC(H)P h }(d cp m p ) (2c): mp 192-195 °C (dec);
1H NMR (CDCl3) δ 7.63 (t, J ) 8.0 Hz, 1H, H4 of pyridine ring),
7.30 (d, J ) 8.0 Hz, 2H, H3,5 of pyridine ring), 7.21-7.15, 6.94-
6.90 (m, 5H, Ph), 5.09 (s, 1H, dCdCH), 3.91 (virtual triplet,
J app ) 4.0 Hz, 4H, PCH2), 2.55-2.47, 2.16-1.45, 1.30-1.14
(each m, 44H, Cy); 13C{1H} NMR (CDCl3) δ 362.0 (t, 2J PC ) 11
Hz, RudCdC), 161.3 (virtual triplet, J app ) 4 Hz, C2,6 of
pyridine ring), 138.5 (s, C4 of pyridine ring), 132.6 (s, C1 of
Ph), 128.0, 126.1, 123.8 (each s, C2-6 of Ph), 120.9 (virtual
triplet, J app ) 4 Hz, C3,5 of pyridine ring), 112.5 (s, RudCdC),
38.1 (virtual triplet, J app ) 11 Hz, C1 of Cy), 34.5 (virtual
triplet, J app ) 10 Hz, PCH2), 29.4, 28.9 (each s, C3,5 of Cy),
27.5, 27.2 (each virtual triplet, J app ) 6 Hz, C2,6 of Cy), 26.0 (s,
2
13C{1H} NMR (CDCl3) δ 340.8 (t, J PC ) 12 Hz, RudCdC),
161.8 (virtual triplet, J app ) 4 Hz, C2,6 of pyridine ring), 138.0
(s, C4 of pyridine ring), 132.1 (s, C1 of Ph), 130.2, 127.3, 125.9
(each s, C2-6 of Ph), 120.5 (br, C3,5 of pyridine ring), 110.3 (s,
RudCdC), 38.2 (virtual triplet, J app ) 10 Hz, C1 of Cy), 34.3
(virtual triplet, J app ) 10 Hz, PCH2), 29.4, 28.8 (each s, C3,5 of
Cy), 27.3, 27.0 (each virtual triplet, J app ) 6 Hz, C2,6 of Cy),
25.8 (s, C4 of Cy), 1.0 (s, SiMe3); 31P{1H} NMR (CDCl3) δ 44.0
(s); IR (KBr) 1600, 1555 cm-1. Anal. Calcd for C42H65Cl2NP2-
RuSi: C, 59.63; H, 7.74; N, 1.66. Found: C, 59.40; H, 7.85; N,
1.69.

Vinylideneruthenium(II) Complexes
Organometallics, Vol. 21, No. 15, 2002 3291
Ta ble 5. Cr ysta llogr a p h ic Da ta a n d Deta ils of
Str u ctu r e Refin em en t for 2c a n d 5a
parameters is reported in Table 5. Single crystals of 2c and
5a , which were grown by slow diffusion of saturated CH2Cl2
solutions into pentane at room temperature, were mounted
on glass fibers with an epoxy resin adhesive. All measurements
were performed at 198 K on a Rigaku AFC5R (for 2c) or
AFC7R (for 5a ) four-circle diffractometer using graphite-
monochromated Mo KR radiation (λ ) 0.71069 Å). Unit cell
dimensions were obtained from a least-squares treatment of
the setting angles of 25 automatically centered reflections with
29° < 2θ < 30° (for 2c) or 25° < 2θ < 29° (for 5a ). Diffraction
data were collected up to the maximum 2θ value of 55.0° using
the ω-2θ scan technique and subsequently corrected for
Lorentz and polarization effects. The data were also corrected
for absorption based on azimuthal scans of three standard
reflections. No significant decay in the standard reflections was
noted throughout the measurements.
2c
5a
formula
fw
C39H57Cl2NP2Ru‚CH2Cl2 C42H65Cl2NP2RuSi
858.74
845.99
cryst size (mm)
cryst syst
space group
a (Å)
b (Å)
c (Å)
0.4 × 0.3 × 0.3
triclinic
P1h (No. 2)
12.708(2)
14.262(1)
12.386(1)
96.413(9)
112.023(8)
95.48(1)
2045.0(4)
2
0.2 × 0.2 × 0.2
monoclinic
P21/c (No. 14)
12.303(1)
19.167(1)
17.950(1)
R (deg)
â (deg)
90.343(7)
γ (deg)
V (Å3)
4232.9(6)
4
6.30
1784
Z
µ(Mo KR) (cm-1
F(000)
)
7.52
896
All calculations were performed with the Texsan Crystal
Sturucture Analysis Package provided by Rigaku Corp. The
scattering factors were taken from ref 21. The structures were
solved by heavy atom Patterson methods (PATTY)22 and
expanded using Fourier techniques (DIRDIF94).23 Each struc-
ture was refined by full-matrix least-squares with anisotropic
thermal parameters for all non-hydrogen atoms. In the crystal
structure of 2c, the solvent molecules (CH2Cl2) were observed
to be statically disordered. They were modeled with three
different CH2Cl2 moieties and refined with complementary
occupancy factors. In the final cycles of refinement, hydrogen
atoms were located at idealized positions (d(C-H) ) 0.95 Å)
with isotropic temperature factors (Biso ) 1.20Bbonded atom) and
were included in calculation without refinement of their
parameters. The function minimized in least-squares was
2θmax (deg)
T (K)
55.0
198
55.0
198
transmn factor
scan width (deg) 1.37 + 0.35 tan θ
scan type
0.92-1.00
0.94-1.00
1.31 + 0.35 tan θ
ω-2θ
ω-2θ
16
scan rate (deg
16
min-1
)
no. reflns measd 9760
no. unique reflns 9385
10151
9710
(Rint ) 0.033)
(Rint ) 0.022)
6442 (I g 3σ(I))
443
no. observations 5888 (I g 3σ(I))
no. variables
463
Ra
Rw
0.079
0.125
1.18
0.054
0.091
1.18
b
GOFc
max ∆/σ in final 0.006
cycle
0.000
∑w(Fo - Fc2)2 (w ) 1/[σ2(Fo2)]).
2
max. and min.
1.18, -0.90
0.52, -0.35
peak (e Å-3
)
Su p p or tin g In for m a tion Ava ila ble: Details of the struc-
ture determination of 2c and 5a , including a figure giving the
atomic numbering scheme and tables of atomic coordinates,
thermal parameters, and full bond distances and angles. This
material is available free of charge via the Internet at
http://pubs.acs.org.
R ) ∑(Fo - Fc2)/∑Fo2. Rw ) [∑w(Fo - Fc2)2/∑w(Fo2)2]1/2, w
) 1/[σ2(Fo2)]. c GOF ) [∑w(|Fo| - |Fc|)2/(No - Np)]1/2, where No is
the number of observations and Nv the number of variables.
a
2
b
2
Ru Cl2{dCdC(SiMe3)2}(d cp m p ) (5b): reddish brown solid
1
(65%); mp 215-219 °C (dec); H NMR (CDCl3) δ 7.52 (t, J )
OM020238R
7.8 Hz, 1H, H4 of pyridine ring), 7.21 (d, J ) 7.8 Hz, 1H, H3,5
of pyridine ring), 3.82 (virtual triplet, J app ) 3.9 Hz, 4H, 2
PCH2), 2.66-2.44, 2.01-1.57, 1.29-1.11 (each m, 44H, 2 PCy2),
0.25 (s, 18H, SiMe3); 13C{1H} NMR analysis of this complex
was not feasible due to its low solubility; 31P{1H} NMR (CDCl3)
(21) Cromer, D. T.; Waber, J . T. International Tables for X-ray
Crystallography; The Kynoch Press: Birmingham, UK, 1974; Vol. IV.
(22) Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.;
Garcia-Granda, S.; Gould, R. O.; Smits, J . M. M.; Smykalla, C. The
PATTY and DIRDIF Program System; Technical Report of the Crystal-
lographic Laboratory; University of Nijmegen: Nijmegen, The Neth-
erlands, 1992.
(23) Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.;
de Gelder, R.; Israel, R.; Smits, J . M. M. The DIRDIF-94 Program
System; Technical Report of the Crystallographic Laboratory; Univer-
sity of Nijmegen: Nijmegen, The Netherlands, 1994.
δ 40.9 (s); IR (KBr) 1605, 1560 cm-1. Anal. Calcd for C39H69
Cl2NP2RuSi2: C, 55.63; H, 8.26; N, 1.66. Found: C, 56.33; H,
8.18; N, 1.69.
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Cr ysta l Str u ctu r e Deter m in a tion of 2c a n d 5a . A
summary of crystal data, intensity collection, and refinement